Guidance on Best Available Techniques and Best Environmental Practices for the Use of Perfluorooctane Sulfonic Acid (PFOS) and R

Guidance on best available techniques and best environmental practices for the use of perfluorooctane sulfonic acid (PFOS) and related chemicals listed under the Stockholm Convention on Persistent Organic Pollutants

Note by the Secretariat: Substantive input and specific comments received from parties and others have been integrated in this draft. General comments requiring additional information which has not been made available to the Secretariat have not yet been addressed. The list of comments and responses is provided in a separate document.

Draft – 5219 Septe Octomber 2014 Revised March 2014 Formatted: Left

Formatted: List Paragraph Formatted: Indent: Left: 2"

Disclaimer

The views expressed in this publication do not necessarily reflect the views of the Secretariat of the Stockholm Convention (SSC), the United Nations Environment Programme (UNEP), the United Nations Industrial Development Organization (UNIDO), the United Nations Institute for Training and Research (UNITAR), the United Nations (UN) or other contributory organizations. SSC, UNEP, UNIDO, UNITAR or the UN do not accept responsibility for the accuracy or completeness of the contents and shall not be liable for any loss or damage that may be occasioned, directly or indirectly, through the use of, or reliance on, the contents of this publication.

Comment [A1]: Please consider updating the Table of Contents Table of Contents according to suggested new structure of the document. An outline for Chapter 3 and 4 can be found Table of Contents ...... 43 after Chapter 2 concludes. List of Figures ...... 45 Abbreviations and Acronyms ...... 56 1. Introduction ...... 78 1.1 Purpose ...... 78 1.2 Structure and use of this document ...... 78 1.3 Perfluorooctane sulfonic acid, its salts, and perfluorooctane sulfonyl fluoride ...... 88 1.3.1 Chemicals listed in Part III of Annex B of the Convention ...... 88 1.3.2 Characteristics ...... 88 1.3.3 Risks ...... 88 1.3.4 Production and uses ...... 89 2. Process descriptions of current and alternative chemistry and processes ...... 1011 2.1 Coated and impregnated items ...... 1111 2.1.1 Introduction ...... 3011 2.1.2 Textiles, paper and leather ...... 3013 2.1.3 Carpets ...... 3215 2.1.4 Paper and packaging ...... 3216 2.2 Insecticides ...... 3616 2.2.1 Introduction ...... 3616 2.2.2 Current insecticides for control of red imported fire ants and termites ...... 3616 2.2.3 PFOS-related substances and alternative pesticides for the control of leaf-cutting ants ...... 3616 2.3 Aviation hydraulic fluids ...... 3617 2.3.1 PFOS and alternative chemistry ...... 3617 2.4 Fire fighting foams ...... 3617 2.4.1 Finishing processes ...... 3617 2.4.2 Types of foams ...... 3618 2.4.3 Choosing an AFFF ...... 3618 2.5 Decorative and hard metal plating processes ...... 3619 2.5.1 PFOS and alternative chemistry ...... 3619 2.5.2 Electroplating of plastics ...... 3619 2.5.3 Rubber and plastic products ...... 3619 2.6 Chemically driven oil and gas production ...... 3619 2.6.1 PFOS and alternative chemistry ...... 3619 2.7 Electronics industry ...... 3620 2.7.1 PFOS and alternative chemistry ...... 3620 2.7.2 Semiconductor industry ...... 3621 2.7.3 Photographic industry ...... 3623 3. BAT/BEP principles for chemicals management of PFOS ...... 5924 3.1 General BAT/BEP measures ...... 5924 3.1.1 Storage, handling, dosing, dispensing and transport of PFOS . 5924 3.1.2 Improved knowledge of the raw materials used ...... 5924 3.1.3 Minimization/optimization of the chemicals used ...... 5924

3.1.4 Equipment ...... 5925 3.2 Water management, off-gas and solid waste management . 5925 3.3 Handling and knowledge of the waste flow ...... 5926 3.3.1 Pre-acceptance procedure ...... 5926 3.3.2 Acceptance procedure ...... 5926 3.3.3 Sampling procedures ...... 5927 3.3.4 Reception facility ...... 5927 3.4 Occupational health and safety measures ...... 5928 3.4.1 PFOS Handling precautions ...... 5928 3.4.2 Special and personal protection: PFOS ...... 5929 3.4.3 First aid procedures ...... 5929 4. Specific BAT/BEP measures by process category ...... 5930 4.1 Coated and impregnated Items ...... 5930 4.1.1 Minimization/optimization of chemicals used ...... 5930 4.1.2 Application of hydrophobic finish of textiles and upholstery .. 5930 4.2 Insecticides ...... 5931 4.3 Fire fighting foam ...... 5932 4.3.1 Inventory management ...... 5933 4.3.2 Training with foams ...... 5933 4.3.3 Prevention of unintended releases ...... 5933 4.3.4 Response to a release ...... 5934 4.3.5 Management of residual (waste) materials ...... 5935 4.4 Decorative and hard metal plating process ...... 5936 4.4.1 Chromium-VI-electrolytes in decorative and hard metal plating5936 4.4.2 Electroplating of plastics ...... 5937 4.4.3 Further electroplating systems ...... 5937 4.4.4 Measures to avoid or reduce emissions of PFOS into the environment ...... 5937 4.4.5 Removal of PFOS from the wastewater ...... 5939 4.4.6 PFOS and alternative chemistry ...... 5941 4.5 Chemically driven oil and gas production ...... 5942 4.5.1 Well stimulation procedures ...... 5942 4.6 Semiconductor industry ...... 5943 4.6.1 Leakage recovery ...... 5943 4.6.2 Storage of PFOS-containing product ...... 5943 4.6.3 Indication of storage location ...... 5944 4.6.4 Transport ...... 5944 4.6.5 Refill ...... 5944 4.6.6 Measures for equipment that uses PFOS ...... 5944 4.6.7 Measures to deal with leakage of a container storing PFOS or during refill ...... 5945 4.6.8 Confirmation of release amounts of PFOS ...... 5945 4.7 Photographic industry ...... 5945 4.7.1 Measures pertaining to photographic developing work ...... 5945 5. Guidance/Guidelines on Best Environmental Practices ...... 5946 5.1 Environmental management systems ...... 6346 5.2 Additional EMS considerations ...... 6347 5.3 Specific education and training of employees ...... 6347 5.4 Industrial considerations ...... 6347 5

References 6449

List of Figures : General principle for the pad dry cure process ...... 14 Figure 2-1 : PFOS use in electronics industry supply chain ...... 21 Figure 2-2 : Different steps in semiconductor manufacturing where PFOS Figure 2-3 is used as an intermediate ...... 21 : Description of photoresist critical use of PFOS and its related Figure 2-4 substances in photolithography processes ...... 22 : Description of anti-reflective coating critical use of PFOS and Figure 2-5 its related substances in photolithography processes ...... 23

Comment [A2]: Might need to be updated Abbreviations and Acronyms once all updates in the text are complete ABS acrylonitrile butadiene styrene AFFF aqueous film-forming foam APEO Alkylphenoletoxylates AR-AFF alcohol resistant aqueous film-forming foam ARC anti-reflective coating AR-FFFP alcohol-resistant film-forming fluoroprotein AR-FP alcohol-resistant fluoroprotein Foam BARC bottom anti-reflective coating BAT best Best available Available Ttechniques BEP best Best Environmental Environmental practicesPractice BOD5 5-Day biochemical oxygen demand BPM barrels per minute BREF BAT Reference Document CCD charge-coupled device (technology for capturing digital images) CMC critical micelle concentration COD chemical oxygen demand COP Conference of Parties DUV deep ultra violet DWR durable water-repellent ECF electrochemical fluorination EMS environmental management system ETFE TetrafluoroethyleneEthylene-tetrafluoroethylene cpolymer EtFOSA N-Ethyl perflurooctane sulfonamidesulfonamide FFFP film-forming fluoroprotein foam FOSA N-Alkylperfluorooctanesulfphonamide FOSE N-Alkylperfluorooctanesulfphonamidoethanol FP fluoroprotein foam IBC intermediate bulk container INPEV National Institute for Processing of Empty Packages LCD liquid crystal display MSDS material safety data sheet PBT persistencePersistent, bioaccumulation Bioaccumulative and Ttoxicity PFAS perflouroalkyl sulphonate PFBS perfluorobutane sulfphonate PFC perfluorinated compound PFOS perfluorooctane sulfonic acid PFOSA perfluorooctanesulfphonic acid PFOSF perfluorooctanesulphonyl fluoride PFSA perfluoroalkane sulfonic acid POPRC Persistent Organic Pollutant Review Committee POPs persistent organic pollutants

PPE personal protective equipment PVD physical vapour deposition R&D research & development SDS Safety Data Sheet STMP surface treatment of metals and plastics TARC top anti-reflective coating THPFOS tetrahydro PFOS TLV threshold limit value UNEP United Nations Environment Programme US EPA United States Environmental Protection Agency VOC volatile organic compounds

1. Introduction Comment [A3]: Please consider to include the 1.1 Purpose added sentence as it makes clear that this is not The concept of best Best available Available Ttechniques (BAT) and Best Environmental Practices a comprehensive overview of all available (BEP) is not aimed at the prescription of any specific technique technology or alternative techniques. practicetechnology. BAT means the most effective and advanced techniques available in addition to the practical suitability of particular techniques. Best environmental Environmental practices Practices (BEP) describe the application of the most appropriate combination of environmental control measures and strategies (Article 5, f (v) of the Stockholm Convention). As such this document aims to include best available information on these topics. However, the content of each chapter might not be comprehensive. The Parties should consider reaching out to (inter)national industry associations representing the chemical suppliers and the different industrial users addressed in this report for further information on (additional) alternatives that relate to both BAT and BEP. Article 3, paragraph 6 of the Stockholm Convention, requests Parties that have a specific exemption and/or acceptable purpose to take measures to ensure that any production or use under such exemption or purpose is carried out in a manner that prevents or minimizes human exposure and releases to the environment (i.e. BAT/BEP practices). This guidance document has been developed to guide Parties in adequately addressing the risks of perfluorooctane sulfonic acid (PFOS) and its related substances and to identify suitable alternative candidates. In general, producers and users of chemicals should follow good chemical management practices and implement the Best Available Techniques (BAT) and Best Environmental Practices (BEP) at their facilities to avoid unnecessary emissions of chemicals to the environment. A hazard-based assessment of the identified alternatives to PFOS and PFOS-related substances will be publicly available by the end of October 2014; for a draft version, please see [ ]. It is Comment [A4]: http://chm.pops.int/TheConven strongly recommended that further assessment of such alternatives is carried out within each tion/POPsReviewCommittee/tabid/3502/Default.as px Party’s national framework of authorization. In addition, substances which have been identified in that assessment as Class 4, may still exhibit hazardous characteristics. These should be Formatted: Font: +Body assessed by Parties before considering such substances as a suitable alternative. Formatted: Font: +Body Formatted: Font: +Body

1.2 Structure and use of this document Formatted: Font: +Body Chapter 1 outlines the purpose and structure of this document. It also includes a brief Formatted: Font: +Body description of the characteristics and uses of PFOS and PFOS-related substances, directly Formatted: Font: +Body relevant provisions of the Stockholm Convention (Article 5, Annexes B and C) and a summary of required measures under these provisions. Comment [A5]: Please consider to structure the document in a way that it flows according to Chapter 2 provides a brief description of the various processes in which PFOS and PFOS-related „Acceptable Purpose“ and „Specific Exemption“ and the listed industries therein. Please see a substances areis used and provides guidance on the consideration of alternatives (BAT) for these suggestion for numbering in Table 1. processes. Subsequently, please consider inserting two Chapter 3 includes general Best Available Techniques (BAT) and Best Environmental Practice Tables 2 and 3 that summarize the findings whether or not alternatives exist for Acceptable (BEP) guidance for chemical management, including for PFOS and PFOS-related substances, Purpose (Table 2) and Specific Exemption applicable principles and descriptions of considerations that cut across multiple process (Table 3) categories. It would be excellent to have the opportunity to compare the updated information in this Chapter 4 contains specific BAT/BEP guidance for the process categories listed in chapter 2. document with the Parties‘ input to the National Reporting System on „progress made to eliminate“ which will be available after August 31, 2014. 9

Chapter 5 provides general guidance on best Best environmental Environmental practices Practices (BEP) for the management of PFOSchemicals.

1.3 Perfluorooctane sulfonic acid, its salts, and perfluorooctane sulfonyl fluoride 1.3.1 Chemicals listed in Part III of Annex B of the Convention PFOS is a fully fluorinated anionic substance, which is commonly used as a salt or as the acid in some applications or is a degradation product ofincorporated PFOS-related building blocks ofinto larger molecules, such as polymers. PFOS and its closely related compounds, which may contain PFOS impurities or substances that can result indegrade to PFOS, are members of the large family of perfluoroalkaneyl sulfonic acidsate (PFSAsAS) substances. Comment [A6]: Please include the following references: ”Synthesis Paper on Per- and 1.3.2 Characteristics Polyfluorinated Chemicals (PFCs)”, OECD/UNEP Global PFC Group, June 2013; PFOS is very persistent, and has substantial bioaccumulations and biomagnifying properties and http://www.oecd.org/env/ehs/risk- is toxic., Aalthough it does not follow the classic pattern of other POPs by partitioning into fatty management/PFC_FINAL-Web.pdf And tissues; instead, it binds to proteins in the blood and liver. It has a capacity to undergo long- Buck, R. C.; Franklin, J.; Berger, U.; Conder, J. M.; range transport and also fulfils the toxicity criteria of the Convention. Cousins, I. T.; De Voogt, P.; Jensen, A. A.; Kannan, K.; Mabury, S. A.; van Leeuwen, S. P. J. Perfluoroalkyl 1.3.3 Risks and polyfluoroalkyl substances in the environment: terminology, classification, and origins. Integr At its second meeting, the Persistent Organic Pollutants Review Committee (POPRC) adopted Environ Assess Manag 2011, 7, 513–541; Open Access Publication: the "“risk profile"” on perfluorooctane sulfonate. At its third meeting, the POPRC adopted the http://onlinelibrary.wiley.com/doi/10.1002/ieam.25 "“risk management evaluation"” on perfluorooctane sulfonate. For more information on the 8/full risks posed by PFOS, these documents can be found in the "“New POPs"” section at www.pops.int. 1.3.4 Production and uses PFOS and PFOS-related substances are listed under Part I of Annex B of the Convention and Part III specifically addresses issues related to these chemicals. Production and use shall be eliminated by all Parties except Parties that have notified the secretariat to produce/or use them according to the possible specific exemptions and acceptable purposes described in Annex B, Part I. So, PFOS and PFOS-related substances areis still produced and used in several countries. The list of uses for acceptable purposes or specific exemptions in the Convention is given below in the Ttable 1 below. All other uses of these compounds are banned under the The use categories not listed in the Convention [see e.g.]. are banned uses, and Acceptable Purpose uses Comment [A7]: Guidance for the Inventory of and Specific Exemption uses were identified and described in the Guideline on Alternatives to Perfluorooctane Sulfonic Acid (PFOS) and Related Chemicals Listed under the Stockholm Convention on Perfluorooctane Sulfonate and its Derivatives developed under the POPs Review Committee Persistent Organic Pollutants (PFOS Inventory (UNEP/POPS/POPRC.6/13/Add.3, 2010). In its decision SC-5/5, the Conference of the Parties to Guidance; Secretariat of the Stockholm Convention, the Stockholm Convention requested the Persistent Organic Pollutants Review Committee to 2012) develop a technical paper on the identification and assessment of alternatives to the use of Comment [A8]: A newer version exists UNEP/POPS/POPRC.9/INF/11/Rev. 1. Can perfluorooctane sulfonic acid (PFOS) and PFOS-related substances in open applications. The you please insert a link to the most recent technical paper will be considered by the Committee at its eighth meeting, October 2012. The document? Please include information that this document might be further revised as a result of information provided in the technical paper on the identification and assessment of alternatives the POPRC-10 review. to the use of PFOS and PFOS-related substances in open applications is set out in document UNEP/POPS/POPRC.8/INF/17. Please note, the content of each chapter in the two documents Comment [A9]: Please provide a link to the referenced above might not be comprehensive. The Parties should consider reaching out to most recent document. (inter)national industry associations representing the chemical suppliers and the different

industrial users addressed in this report for further information on (additional) alternatives that relate to both BAT and BEP.

Table 1: Acceptable Purpose and Specific Exemptions uses for PFOS, its salts and PFOSF (in the text referred to as “PFOS and PFOS-related substances”) as listed in Annex B of the Stockholm Convention.

1. Acceptable purposes 2. Specific exemptions Formatted: Font: (Default) Calibri, Kern at 16 pt A. Photo-imaging I. A. Photo masks in the semiconductor Formatted: Font: (Default) Calibri, 11 pt, B. Photoresist and anti-reflective coatings and liquid crystal display (LCD) industries Bold, Font color: Background 1, Kern at 16 pt for semiconductors J. B. Metal plating (hard metal plating) Formatted: List Paragraph, Numbered + C. Etching agent for compound K. C. Metal plating (decorative plating) Level: 1 + Numbering Style: 1, 2, 3, … + Start at: 1 + Alignment: Left + Aligned at: 0.25" + semiconductors and ceramic filters L. D. Electric and electronic parts for some Indent at: 0.5" D. Aviation hydraulic fluids colour printers and colour copy machines Formatted: Font: (Default) Calibri, Kern at 16 E. Metal plating (hard metal plating) only M. E. Insecticides for control of red pt in closed-loop systems imported fire ants and termites Formatted: Font: (Default) Calibri, 11 pt, F. Certain medical devices (such as N. F. Chemically driven oil production Bold, Font color: Background 1, Kern at 16 pt ethylene tetrafluoroethylene copolymer O. G. Carpets Formatted: Font: (Default) Calibri (ETFE) layers and radio opaque ETFE P. H. Leather and apparel Formatted: Indent: Left: 0.25", No bullets or production, in-vitro diagnostic medical numbering Q. I. Textiles and upholstery devices, and CCD colour filters) Formatted: Font: (Default) Calibri, 11 pt R. K. Paper and packaging G. Fire fighting foam Formatted: Indent: Left: 0.25", No bullets or H. Insect baits for control of leaf-cutting S. L. Coatings and coating additives numbering ants from genus Atta spp. aAnd T. M. Rubber and plastics Formatted: Font: Italic Acromyrmex spp.

Although alternatives to PFOS are available for some applications, as described in the chapter 2, this is not always the case in developing countries, where they still need to be phased in. Some applications like photo imaging, use for semiconductors or aviation hydraulic fluids are considered as acceptable purposes, partly because technically feasible alternatives to PFOS have not been well established to date. Comment [A10]: These two paragraphs are not needed. The purpose of this document is to For an illustration of major product categories and applications of PFOS, see the Guidance for help Parties implement their NIP; contents of the second paragraph are summarized in Table the Inventory of Perfluorooctane Sulfonic Acid (PFOS) and Related Chemicals Listed under the 2 (that has been suggested to be included). Stockholm Convention on Persistent Organic Pollutants (PFOS Inventory Guidance; Secretariat of the Stockholm Convention, 2012). Comment [A11]: Reference to this document was made earlier in the chapter. Suggest to delete this paragraph.

2. Process descriptions of current and alternative Comment [A12]: We suggest to split the chemistry and processes chapter into 2.1. Addressing Acceptable This chapter provides brief descriptions of the different processes involving PFOS and related Purpose and 2.2. Addressing Speciifc Exemptions substances and the – if available - viable alternative chemistry to PFOS and PFOS-related substances for each described process. The processes described are for those where production and use is allowedlisted in Table 1. Information on alternative processes is also given under each process description. Each chapter aims to identify BAT as “Fluorinated Alternatives”, “Non- Fluorinated Alternatives” and “Alternative Technology”.

Many For most processes the use ofusing PFOS and PFOS-related substances isare no longer needed and alternatives have been identified are in use. Please see Table 2 for a summary of key findings for “Acceptable Purpose” applications and please Table 3 for a summary of key findings for “Specific Exemption” applications. Please note, More more specific chemical information on alternatives to PFOS and PFOS-related substances can be found in the Guidance on Alternatives to Perfluorooctane Sulphonate and its Derivatives (UNEP/POPS/POPRC.6/13/Add.3, 2010), and and in the Technical Paper [ ].. A hazard-based Comment [A13]: See above, please update assessment of the identified alternatives will be publicly available by the end of October 2014 with more recent link to the document. [please insert web-link here]. It is strongly recommended that further assessment is carried out Comment [A14]: Insert reference to most recent version within each Party’s national framework of authorization. In addition, substances which have Comment [A15]: Please provide link to most been identified in that assessment as not likely to be a POP (Class 4), may still exhibit hazardous recent document characteristics that should be assessed by Parties before considering such substances as a suitable alternative. Please note, this document aims to include best available information on these topics. However, the content of each chapter might not be comprehensive. The Parties should consider reaching out to (inter)national industry associations representing the chemical suppliers and the different industrial users addressed in this report for further information on (additional) alternatives that relate to both BAT and BEP. The BAT options listed in the following chapters might not work as “drop-in” replacements and Formatted: Adjust space between Latin and might therefore require some reformulation work at the user site with assistance from the Asian text, Adjust space between Asian text and numbers chemical supplier.

Table 2: Summary of key findings for “Acceptable Purpose” applications (*: applies to new uses only; **: identified BATalternative technology might yield increased human and environmental exposure).

Acceptable Formatted Table Acceptable Specific Alternative Alternative ExemptionChemical Technology Technology Identity and Exists Acceptable Purpose Chemistry Properties of Exists Acceptable [Yes/No]Trade Alternatives Names and [Yes/No] [Known/Not Producers

Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Known] [Known/Not Formatted ... Known] Formatted ... KNOWNPhoto Formatted ... masks in the Formatted ... semiconductor and 1. Photo-imaging Formatted ... A YES liquid crystal NOT KNOWN display (LCD) Formatted ... industries Formatted ...

Formatted ... Metal plating (hard Formatted ... Photoresist and anti- metal plating)NOT reflective coatings for Formatted ... B YES* KNOWN NOT KNOWN semiconductors Formatted ... Formatted ... Formatted KNOWN ... Formatted Etching agent for ... NOT KNOWNMetal NOT KNOWN Formatted compound semiconductors YES ... C plating (decorative and ceramic filters NOT KNOWN Formatted ... YES plating) Formatted ... Formatted ... N/AElectric and Formatted electronic parts for ... some colour Formatted ... Aviation hydraulic fluids NO N/A D printers and colour Formatted ... copy machines Formatted ...

Formatted ... Insecticides for Formatted ... Metal plating (hard metal control of red plating) only in closed-loop Formatted ... E NOT KNOWN imported fire ants N/A systems and termitesN/A Formatted ... Formatted ... Formatted Certain medical devices KNOWN ... (such as ethylene Formatted ... YES NOT KNOWN NOT KNOWN tetrafluoroethylene NOT KNOWN Formatted ... copolymer (ETFE) layers and NOT KNOWN NOT KNOWN NOT Formatted ... F radio opaque ETFE KNOWNChemically NOT KNOWN NOT KNOWN Formatted ... production, in-vitro driven oil diagnostic medical devices, YES production NOT KNOWN Formatted ... and CCD colour filters) Formatted ...

Formatted ... Carpets Fire fighting foam Formatted ... G YES KNOWN KNOWN Formatted ... Formatted Insect baits for control of leaf- Leather and ... H cutting ants from genus Atta spp. YES** apparelN/A N/A Formatted ... And and Acromyrmex spp. Formatted ... Formatted Textiles and ... upholstery Formatted ... Formatted ... 13 Formatted ...

Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ...

Formatted ... Paper and Formatted ... packaging Formatted ... Formatted ... Coatings and coating Formatted additives ... Formatted ... Rubber and plastics Formatted ...

Formatted ... Table 3: Summary of key findings for “Specific Exemption” applications (*: alternative(s) might Formatted ... be less effective than incumbent and/or can only be used for certain applications). Formatted ... Formatted ... Acceptable Identity and Formatted ... Properties of Trade Names Alternative Formatted ... Acceptable and Producers Technology Formatted ... Specific Exemption Alternatives Chemistry [Known/Not Formatted ... Exists [Known/Not Known] Formatted ... [Yes/No] Known] Formatted ... Photo masks in the Formatted ... A semiconductor and liquid YES* NOT KNOWN NOT KNOWN Formatted ... crystal display (LCD) industries Metal plating (hard metal Formatted ... B YES* KNOWN KNOWN plating) Formatted ... Metal plating (decorative Formatted YES* KNOWN NOT KNOWN ... C plating) Formatted ... Electric and electronic parts for Formatted Table D some colour printers and NOT KNOWN NOT KNOWN NOT KNOWN ... colour copy machines Formatted ... Insecticides for control of red Formatted E YES KNOWN KNOWN ... imported fire ants and termites Formatted ... Chemically driven oil YES KNOWN NOT KNOWN Formatted ... F production Formatted G Carpets YES KNOWN KNOWN ... Formatted H Leather and apparel YES KNOWN KNOWN ... Formatted I Textiles and upholstery YES KNOWN KNOWN ... Formatted K Paper and packaging YES KNOWN KNOWN ... Formatted L Coatings and coating additives YES KNOWN KNOWN ... Formatted M Rubber and plastics YES KNOWN NOT KNOWN ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... Formatted ... 14 Formatted ...

2.1. Best Available TechnologyAlternative Chemistry (BAT) for “Acceptable Purpose” Applications

Comment [A16]: As defined in Annex B of the Photo-Imaging Stockholm Convention 2.1.A. The text in chapter has been modified by including sections copied from the Guidance Background: document. Slight edits to that text have been made. In the photographic industry PFOS-related substances have been used in manufacturing of Formatted: Heading 3, Left, Don't adjust space between Latin and Asian text photographic film, papers and printing plates. These PFOS-based chemicals have been used for the following purposes in mixtures for coatings (RPA association, 2004): Formatted: Font: Bold • Surfactants Formatted: Font: (Default) Lucida Sans Unicode, Bold • Electrostatic charge control agents Formatted: Font: (Default) Lucida Sans • Friction control agents Unicode, Bold • Dirt-repellent agents Formatted: Font: (Default) Lucida Sans Unicode, Bold, Font color: Auto • Adhesion control agents Formatted: Font: 12 pt Formatted: Font: 12 pt, Bold Best Available Technology (BAT)Alternative Chemistry for PFOS and PFOS- Formatted: Font: 14 pt, Bold Related Substances Formatted: Font: 12 pt, Bold, Font color: Text In the past, PFOS-related substances such as tetraethylammonium perfluorooctane sulfonate 2 and perfluorooctyl sulfonamidopropyl quaternary ammonium iodide have been used in the Formatted: Font: 12 pt, Bold, Font color: Text range of 0.1–0.8 µg/cm2. 2 Comment [A17]: Updates include text copied from the Guidance document and the Technical Fluorinated Alternatives: Paper with some slight edits. • Short-chain fluorotelomer-based products Formatted: Font: Bold, Font color: Text 2 • C3 and C4 (perfluorobutane sulfonate)-based compounds Formatted: Font: Bold, Font color: Text 2

Non-Fluorinated Alternatives: Formatted: Font: Not Bold • Hydrocarbon surfactants • Silicone products1

Alternative Technology: • Digital techniques

With fully capable and acceptable alternative technologies commercially available worldwide and in use, there is no need to use PFOS, PFOS-derived, -containing or –releasing chemistry in photo-imaging. Suppliers to this industry as well as users of chemicals in this industry should follow BAT and BEP practices so that emissions to the environment are minimized.

1 There are cosiderable datagaps of siloxane compounds used on the market for photographic applications, see reference UNEP/POPS/POPRC.8/INF/17/Rev.1.

Formatted: Font color: Text 2 2.1.B. Photoresist and Anti-Reflective Coatings for Comment [A18]: Correct title according to the Semiconductors Convention

Background: Semiconductor manufacturing comprises up to 500 steps, involving four fundamental physical Updates in this entire section include text copied from the Guidance document and the processes: Technical Paper with some slight edits.

• Implant Formatted: Font: 12 pt, Bold, Font color: Text • Deposition 2 • Etch Formatted: Font: Bold, Font color: Text 2 • Photolithography Photolithography is the most important of the four processes. It is essential for the successful implementation of the other three processes and, indeed, the overall production process. It shapes and isolates the junctions and transistors; it defines the metallic interconnects; it delineates the electrical paths that form the transistors; and it joins them together. Photolithography reportedly represents 150 of the total 500 steps. Photolithography is also integral to the miniaturization of semiconductors (RPA association, 2004). PFOS reduces the surface tension and reflection of solutions, properties that are Formatted: Body Text, Left, Space After: 0 important for precise photolithography in the semiconductor industry (photoresists and photo pt, No bullets or numbering masks (see chapter under “Specific Exemption”)).

Photoresists are photosensitive polymeric materials used for making circuit patterns. Comment [A19]: Text is copied (with minor edits) from Annex F Questionnaire submitted by Photoresists for fine patterning need to contain a substance called photoacid generator (PAG) Japan on Feb. 9, 2007. that include PFOS. PAG generates hydrogen ions by exposure to laser light which causes an http://chm.pops.int/TheConvention/POPsReviewCo anisotropic chain reaction that increases focal depth. Therefore, PAGs are essential to fine mmittee/Meetings/POPRC2/AnnexFinformationYea r2007/tabid/466/Default.aspx patterning. In subsequent steps photoresist agent is rinsed out during the photolithographic process, PFOS does not remain in semiconductors. Since diffused reflection would possibly disorder the shape of a circuit in design, therefore an anti-reflective coating is necessary to avoid disturbance during photolithographic processes. PFOS is used in anti-reflective coating agents to give surface activity and regulate reflective characteristics of the coating between the metal and resist layers. A number of resist suppliers sell top anti-reflective coating (TARC) and bottom anti-reflective coating (BARC), which are used in combination with deep ultra violet (DUV) photoresist. The process involves placing a thin, top coating on the resist to reduce reflective light, in much the same way and for the same purposes that eyeglasses and camera lenses are coated. Since anti-reflective coating agents are rinsed out during the photolithographic process, PFOS does not remain in the semiconductors. Formatted: Font: 12 pt, Font color: Text 2 Best Available Technology (BAT)Alternative Chemistry for PFOS and PFOS- Formatted: Font: 12 pt, Font color: Text 2

Related Substances Comment [A20]: Updates include text copied “The industry continues to work towards developing comprehensive PFOS substitutes for from the Guidance document and the Technical current and future semiconductor manufacturing. From discussions with suppliers we know that Paper with some slight edits. the manufacturers who synthesize and supply PFOS to the photolithography chemical suppliers Formatted: Font color: Text 2 have terminated production of these PFOS materials. The WSC (World Semiconductor Council) manufacturers have agreed not to seek new uses of photolithography chemicals containing PFOS and the suppliers have publically stated that they will not provide PFOS-containing chemicals for any new uses. Additionally, semiconductor companies are replacing remaining use

of PFOS as the feasibility and capability are proven. A few semiconductor companies will be required to continue to use PFOS blends until these feasibility issues are overcome. The amount left in use is highly controlled.” [WSC, 2011 Report]. Comment [A21]: http://www.semiconductorco uncil.org/wsc/uploads/WSC_2011_Joint_Statem ent.pdf The estimated global annual PFOS use (2010 data) for the three remaining applications is as Annex 2 page 16 - 23 follows [WSC, 2011 Report]: Photoresists: 46.4kg Formatted: Indent: Left: 1", First line: 0.5" BARC: 4.5kg TARC: 893.5kg Formatted: Normal, Indent: Left: 1", First line: 0.5", No bullets or numbering Photoresist and anti-reflectant products are solvent-based solutions containing up to 80% Formatted: Normal, No bullets or numbering solvents with the remaining components being acrylic or other polymer resins, PFOS-derived cross-linking agents, stabilizers and/or PFOS-derived surfactants [ ]. Photoresists and anti- Comment [A22]: http://msdssearch.dow.com/P reflective products that have been formulated without the use of PFOS are commercially ublishedLiteratureDOWCOM/dh_090c/0901b80380 90c227.pdf?filepath=productsafety/pdfs/noreg/233 available but it is not known whether or not these products qualify as BAT for the purposes of -00873.pdf&fromPage=GetDoc this report [for example]. http://msdssearch.dow.com/PublishedLiteratureDO WCOM/dh_08fb/0901b803808fb12

Fluorinated Alternatives: Formatted: Font: +Body, 11 pt Fluorinated compounds are in use. However, information on the type and chemical class of Comment [A23]: http://msdssearch.dow.com/P fluorinated alternatives has not been disclosed. ublishedLiteratureDOWCOM/dh_08fb/0901b80380 8fb120.pdf?filepath=productsafety/pdfs/noreg/233- Non-Fluorinated Alternatives: No information 00827.pdf&fromPage=GetDoc Formatted: Font: Bold Alternative Technologies: No information Formatted: Font: Bold Formatted: Font: Bold No alternative substances have been commercialized for existing uses in PAG, BARC and TARC. However, production of PFOS and PFOS-related substances seems to have ceased for the applications listed here. With production of PFOS and PFOS-related substances ceased to supply the semiconductor industry worldwide, there is no need to further manufacture PFOS, PFOS-derived, -containing or –releasing chemistry for use in new uses photoresists and anti-reflective coatings for semiconductors. Suppliers to this industry as well as users of chemicals in this industry should follow BAT and BEP practices so that emissions to the environment are minimized.

Formatted: Font color: Text 2 2.1.C. Etching Agent for Compound Semiconductors and Comment [A24]: Correct title according to the Ceramic Filters Convention Formatted: Font: 12 pt, Bold, Font color: Text Background 2 Etching Agent for Compound Semiconductors: Formatted: Font: Bold, Font color: Text 2 PFOS has been used as a surfactant in etching processes in the manufacture of compound semiconductors. PFOS was added as part of an etching agent, and rinsed out during the subsequent washing treatment.

Etching Agent for Ceramic Filters: Comment [A25]: Text taken (and slightly edited PFOS has been used in the etching process of piezoelectric ceramic filters which are used as a from input provided to the Secretariat by the Chemical Management Policy Division, bandpass filter at intermediate frequency in two-way radios for police radios, FM radios, TV, Manufacturing Industries Bureau at the Ministry of Remote Keyless Entry Systems for Cars, etc. For deciding on the bandwidth of piezoelectric Economy, Trade and Industry of Japan. ceramic filters, the gap dimension of vibrating electrodes on both sides of the ceramic element is the important indicator. The gap dimension must be controlled within several hundred µm. Because of the possibility of bubble creation in such a minute process, 0.033wt% of PFOS were added to the etching liquid as a surface active agent to prevent bubble creation.

Formatted: Font: 12 pt, Font color: Text 2 Best Available Technology (BAT)Alternative Chemistry for PFOS and PFOS- Formatted: Font: 12 pt, Font color: Text 2

Related Substances Comment [A26]: Updates include text copied Etching Agent for Compound Semiconductors: from the Guidance document and the Technical PFOS was used in this application. Paper with some slight edits. Fluorinated Alternatives: Formatted: Font color: Text 2 According to information provided by the World Semiconductor Council [Insert reference from Formatted: Font color: Text 2 above, WSC 2011] short-chain perfluoroalkyl sulfonates are fluorinated alternatives that are in Comment [A27]: Please insert reference from use today. The use of PFOS has been eliminated for this application. above

Non-Fluorinated Alternatives: No information Formatted: Font: Not Bold Alternative Technology: No information Formatted: Font: Not Bold

With fully capable and acceptable alternative technologies commercially available worldwide and in use, there is no need to use PFOS, PFOS-derived, -containing or –releasing chemistry in etching agents for compound semiconductors. Suppliers to this industry as well as users of chemicals in this industry should follow BAT and BEP practices so that emissions to the environment are minimized.

Etching Agent for Ceramic Filters: PFOS was used in this application in formulations containing 0.033wt%. According to information provided by the Chemical Management Policy Division, Manufacturing Comment [A28]: Please include reference Industries Bureau, Ministry of Economy, Trade and Industry of Japan, the use of PFOS has been from above eliminated for this application. However, the type of alternative substances in use has not been disclosed.

Fluorinated Alternatives: No information Non-Fluorinated Alternatives: No information Alternative Technology: No information Formatted: Body Text

With fully capable and acceptable alternative technologies commercially available worldwide and in use, there is no need to use PFOS, PFOS-derived, -containing or –releasing chemistry in etching agents for ceramic filters. Suppliers to this industry as well as users of chemicals in this industry should follow BAT and BEP practices so that emissions to the environment are minimized.

Formatted: Font: (Default) Calibri Formatted: Body Text

Comment [A29]: Updates include text copied Aviation Hydraulic Fluids from the Guidance document and the Technical Paper with some slight edits.

Background Formatted: Font: 12 pt Aviation hydraulic fluids based on fire resistant alkyl and/or alkyl phenyl phosphate esters Formatted: Heading 2, Don't adjust space contain additives such as the PFOS-related substance potassium salt of perfluoroethylcyclohexyl between Latin and Asian text sulfonate (CAS No. 67584-42-3) in concentrations of about 0.1%. This critical additive provides Formatted: Footer-pool, Indent: Left: 0", First erosion resistance to hydraulic components of the airplane (i.e., valves, actuators, etc.) and line: 0", Space After: 0 pt therefore helps to avoid damage to mechanical parts and significantly extends their operational life. Phosphate-ester based fluids have been used in civil and military airplanes since the 1970s (United States patent 3,679,587 dates from 1972). These fluids are used in applications with performance demands that “oil-based” hydraulic fluids cannot match (e.g., fire resistance and very good low temperature properties).

The total global market for fluorinated compounds in aircraft hydraulic fluids is estimated to be Formatted: Footer-pool, Indent: Left: 0", First about 2 tonnes per year. Annual fluorinated compound consumption in the European Union for line: 0", Space After: 0 pt, Don't adjust space between Latin and Asian text this use was about 730 kilograms/year in 2009.2 Formatted: Font: Times New Roman, 12 pt, (Asian) Japanese (Japan) Best Available Technology (BAT)Alternative Chemistry for PFOS and PFOS- Formatted: Normal, Indent: Left: 0", First Related Substances line: 0", Space After: 0 pt No alternative substances seem to have been commercialized. Therefore, the PFOS-related Formatted: Font: 12 pt, Font color: Text 2 substance potassium salt of perfluoroethylcyclohexyl sulfonate (CAS No. 67584-42-3) represents Formatted: Font: 12 pt, Font color: Text 2 the Best Available Technology (BAT)Chemistry. Comment [A30]: Updates include text copied from the Guidance document and the Technical Suppliers to this industry as well as users of chemicals in this industry should follow BEP Paper with some slight edits. practices so that emissions to the environment are minimized. Formatted: Font color: Text 2 Formatted: Font color: Auto Formatted: Font: Not Bold

Formatted: Font color: Text 2 Metal Plating (hard metal plating) Only in Closed-Loop Systems Formatted: Font: 12 pt, Bold, Font color: Text Background 2 The term “hard” refers to the process of electrodepositing a thick layer (0.2mm or more) of Formatted: Font: Bold, Font color: Text 2 certain types of metal directly onto substrates. In terms of hard chrome plating, for example, the deposited chrome layer provides the following desirable properties: • Hardness • Wearability • Corrosion resistance

2 Dorian Carloni “Perfluorooctane Sulfonate (PFOS) ; Production and Use: Past and Current Formatted: English (United States) Evidence”, UNIDO (2009) http://www.unido.org/fileadmin/user_media/Services/Environmental_Management/Stockholm_Con vention/POPs/DC_Perfluorooctane%20Sulfonate%20Report.PDF Formatted: English (United States) 19

• Lubricity • Low coefficient of friction Examples of hard chrome plated parts are: • Hydraulic cylinders and rods • Railroad wheel bearings and couplers • Molds for the plastic and rubber industry • Tool and die parts The plating process is an electrolytic process that causes mist and bubbles to be ejected from the plating bath containing plating bath solution. This mist is released to the work place environment and will eventually be dispersed into outdoor ambient air unless controlled with add-on air pollution control equipment or chemical fume (mist) suppressants. Chemical fume (mist) suppressants are surfactants that lower the surface tension of the plating solution. While they reduce bubble formation, they also allow for better wetting of the electrolyte at the electrode and allow for better plating bath penetration into patterned articles. The bubbles can cause defects on the plated articles and also cause mist formation. By reducing the surface tension, the created process gas bubbles become smaller and rise more slowly than larger bubbles. Slower bubbles have reduced kinetic energy so that when the bubbles burst at the surface, mist is less likely to be emitted into the air and the droplets fall back onto the plating bath surface. In hard chrome plating and Cr(VI) anodizing tank operations, the plating bath consists of Cr(VI) acid. This acid is a highly oxidative, strong acid that decomposes most types of surfactants. In addition, Cr(VI) is a known human carcinogen and therefore Cr(VI) emissions are regulated to protect workers from occupational exposure and to protect the environment. Emissions to the atmosphere can be reduced by either limiting the amount of Cr(VI) through use of add-on air pollution control devices or utilizing a chemical mist suppressant. Since the plating bath is a highly oxidative environment, PFOS was a suitable surfactant because it is stable under the plating bath conditions. Thus, introduction of PFOS as mist suppressant helped solving occupational safety problems as well as environmental problems relating to Cr(VI) in the hard chrome plating industry. Formatted: Font: (Default) +Body, 11 pt, Font color: Black, (Asian) Chinese (Simplified, PRC), (Other) English (United States) Best Available Technology (BAT)Alternative Chemistry for PFOS and PFOS- Formatted: Font: 12 pt, Font color: Text 2

Related Substances Formatted: Font: 12 pt, Font color: Text 2 From the information available it is unclear whether or not PFOS emissions to the environment can occur from the closed-loop process. Furthermore, it is unclear whether or not PFOS is ever Formatted: Font color: Text 2 exhausted in such application and will need to be replaced. There is not enough information on the current process and on the use of potential alternatives available. The BATbest available alternative chemistry cannot be determined. Formatted: Font: +Body, 11 pt, Not Bold, Font color: Auto Formatted: Normal, Space After: 0 pt

Comment [A31]: Updates in this entire section include text copied from the Guidance Certain Medical Devices document and the Technical Paper with some slight edits. Background Formatted: Font: 12 pt, Bold, Font color: Text Video endoscopes contained a charge-coupled device (CCD) colour filter containing 150ng of 2 PFOS. The CCD is part of technology enabling capturing digital images. Another use of PFOS Formatted: Font: Bold, Font color: Text 2 20

described is as a dispersant of contrast agents that are incorporated into an ethylene- tetrafluoroethylene (ETFE) copolymer layer that is used in radio-opaque catheters.

Formatted: Font: 12 pt, Font color: Text 2 Best Available Technology (BAT)Alternative Chemistry for PFOS and PFOS- Formatted: Font: 12 pt, Font color: Text 2

Related Substances Comment [A32]: Updates include text copied PFOS and PFOS-related substances have been used in critical parts of certain medical devices. from the Guidance document and the Technical Use in ethylene-tetrafluoroethylene (ETFE) copolymer layers: Paper with some slight edits. Fluorinated Alternatives: Formatted: Font color: Text 2 . PFBS replaced PFOS as a dispersant of contrast agents in EFTE layers for radio-opaque Formatted: Font: Not Bold catheters. Non-Fluorinated Alternatives: No information Alternative Technology: No information Formatted: Font: Not Bold

Use in production of radio-opaque ETFE: Fluorinated Alternatives: No information Formatted: Font: +Body, 11 pt Non-Fluorinated Alternatives: No information Formatted: Normal, No bullets or numbering Alternative Technology: No information Formatted: Font: +Body, 11 pt, English Use in certain in-vitro diagnostic devices: (United Kingdom) Fluorinated Alternatives: No information Non-Fluorinated Alternatives: No information Alternative Technology: No information

Use in charge-coupled device (CCD) colour filters: Fluorinated Alternatives: No information Formatted: Normal, No bullets or numbering Non-Fluorinated Alternatives: No information Formatted: Font: +Body, 11 pt Alternative Technology: Formatted: Font: Not Bold . PFOS-free CCD filters are in use

It is unknown whether alternatives to PFOS and PFOS-derived substances for applications such as production of radio-opaque ETFE and use in certain in-vitro diagnostic devices are commercially available. The BATbest available alternative chemistry cannot be determined. With fully capable and acceptable alternative technologies commercially available worldwide and in use for contrast agent dispersants in ETFE layers for radio-opaque catheters and for charge-coupled device (CCD) colour filters, there is no need to use PFOS or PFOS-derived, - containing or –releasing chemistry in certain medical devices. Suppliers to this industry as well as users of chemicals in this industry should follow BAT and BEP practices so that emissions to the environment are minimized.

Fire Fighting Foams Formatted: Font: 12 pt, Bold Background Formatted: Font: Bold Firefighting foams encompass a broad range of products used for the control and Formatted: Font color: Auto extinguishment of Class B combustibles and flammable liquid fuel fires. Class B foam 21

concentrates include those derived from protein bases as well as synthetic or hydrocarbon surfactant based products. Fire fighting foam concentrates are designed primarily for hydrocarbon fuel fire protection and may also include types used for polar solvent or water- miscible fuel fires.

Aqueous film-forming foam (AFFF) is a generic term for fire fighting and/or vapour suppression products used globally to protect both lives and property. This term also encompasses alcohol Formatted: Font color: Auto resistant aqueous film forming foam (AR-AFFF) concentrates. AFFFs are the premier fire fighting foam in many parts of the world and are unique among other fire fighting foams in that they contain a small percentage of fluorinated surfactant (fluorosurfactant). This key ingredient brings unique performance attributes to the product that enable it to be extremely effective in extinguishing fires, preventing re-ignition, and supressing vapour of Class B flammable liquids. AFFF agents are formulated by combining synthetic hydrocarbon surfactants with perfluorinated Formatted: Font color: Auto surfactants. When mixed with water, the resulting solution achieves extremely low surface tension allowing the solution to produce an aqueous film that spreads across a hydrocarbon fuel surface. AFFF products can be used in fixed and portable systems (e.g. sprinkler systems, handheld fire extinguishers, portable cylinders, fire fighting vehicles (fire trucks), etc.). In most situations, AFFF is purchased as a concentrate, typically referred to as “3%” or “6%” depending on its proportioning ratio to be used with water to generate finished expanded foam. Not every situation will necessarily require the use of fire fighting foams. Selection of the correct product can only be determined by a careful consideration of the specific situation at hand (emergency incident or design of life/property protection system) and review of local building codes and other regulations. It is important to remember that foams have proven to be highly effective for their intended purpose. 2.1.1 Types of foams

Foams have been developed for both Class A (ordinary combustibles such as paper and wood) and Class B (flammable liquids) fires. AFFFs were designed to be especially effective in dealing with Class B incidents. Class B foams have two major categories: synthetic foams and protein-based foams. Synthetic foams AFFFs and alcohol-resistant AFFFs (AR-AFFFs) are synthetic foams based on synthetic hydrocarbon and fluorinated surfactants. AR-AFFFs are designed to be effective in the presence of alcohols and other water miscible compounds. This category also encompasses training Formatted: Font color: Auto foams that are used as AFFF and AR-AFFF substitutes in training and system commissioning tests, Class A foams used primarily as wetting agents for Class A fire protection and wildland forestry protection, and other foam concentrates derived from synthetic and hydrocarbon surfactants such as fluorine-free foams. Protein-based foams Protein foams contain substances derived from natural, keratinous proteins such as cow hooves and chicken feathers. These protein hydrolysates are used as foaming agents in protein-based foams, and as such, protein-based foams are generally more biodegradable than synthetic foams. Types of protein-based foams include regular protein foam (P), fluoroprotein foam (FP), film-forming fluoroprotein foam (FFFP), alcohol-resistant fluoroprotein foam (AR-FP), and

alcohol-resistant film-forming fluoroprotein (AR-FFFP). FP, FFFP, AR-FP, and AR-FFFP foams contain levels of fluorosurfactants that significantly improve fire-fighting performance.

Formatted: Font: 12 pt, Font color: Text 2 Best Available Technology (BAT)Alternative Chemistry for PFOS and PFOS- Formatted: Font: 12 pt, Font color: Text 2

Related Substances Formatted: Font color: Text 2 The chemicals used to make the fluorosurfactants that are key ingredients in Class B foams have been manufactured by different processes and have different chemical structures. Prior to 2000, fluorosurfactants used in AFFFs were both PFOS-based and fluorotelomer-based. Although PFOS-based and fluorotelomer-based AFFFs are equally effective, only PFOS-based AFFFs contain PFOS or PFOS precursors. Shortly after the manufacturing phase-out announcement by 3M of PFOS-based products in 2000, PFOS-based AFFFs were generally no longer available within developed countries. The primary supply of AFFF then became fluorotelomer-based. Over the last several years, manufacturers of fluorotelomer-based AFFF have been replacing long-chain (C8 and higher) fluorosurfactants with shorter-chain (C6) fluorosurfactants. Formatted: Font: Calibri, 11 pt, (Asian) Chinese (Simplified, PRC), (Other) English The choice of foam to be used in any specific situation needs to be carefully made, taking into (United Kingdom) consideration multiple factors. It is critically important that the tremendous effectiveness of AFFF products in protecting life and property be considered in making use and system design decisions. Fire protection experts clearly need to have a lead role in making these decisions. When evaluating foam for use in preventing or fighting a fire, several factors could be considered: • Is any type of foam actually needed? For example, in a Class A incident, it may not be necessary to use any foam to control the situation. • If use of a foam is deemed appropriate and/or necessary, does it need to be a Class B foam? For example, while Class B foams may be quite effective on Class A fires, other techniques may be equally effective and more appropriate. • Consideration should be given to using alternative fluids that do not contain fluorinated substances for training and the testing of foam proportioning equipment.

Synthetic and Protein-based Class B Foams: Fluorinated Alternatives: Formatted: Indent: First line: 0.5" Foam manufacturers are currently transitioning to the use of short-chain, fluorotelomer-based surfactants as the key ingredient to produce synthetic Class B foams. Listed below in alphabetical order are the main suppliers of fluorinated surfactants to the fire fighting foam industry with their brand names: Short-chain fluorinated telomer-based surfactants: Chemguard Formatted: Indent: First line: 0.5" DuPont (Capstone®) Dynax

Non-fluorinated Alternatives: Formatted: Indent: First line: 0.5" Non-fluorinated alternatives exist and are in use but often cannot achieve the stringent performance requirements.

Alternative Technology: Formatted: Indent: First line: 0.5" No information

With fully capable and acceptable alternative technologies commercially available and in use worldwide, there is no need to use PFOS, PFOS-derived, -containing or –releasing chemistry in fire fighting foams. Spent Fire Fighting Foam solution has been identified as a point source of fluorinated surfactants emissions to the environment. Suppliers to this industry as well as users of chemicals in this industry should follow BAT and BEP practices so that emissions to the environment are minimized.

Insect Baits for Control of Leaf-Cutting Ants from genus Atta spp. Acromyrmex spp. And Formatted: Font: 12 pt, Bold Background: N-Ethyl perfluorooctane sulfonamide (EtFOSA; CAS No. 4151-50-2), also called sulfluramid, or Formatted: Font: Bold sulfuramid, is both a surfactant and a pesticide used in Brazil for control of leaf-cutting ants from Formatted: Font color: Auto the species Atta spp. and Acromyrmex spp. Sulfluramid was introduced in Brazil in 1992, after verification of its efficiency with many leaf-cutting ant species, replacing the active ingredient dodecachlor. In addition, the following active ingredients are registered and in use in Brazil for the control of leaf-cutting ants: fenitrothion (in the form of thermo-nebulization) and deltamethrin (in powder form). Sulfluramid is the active ingredient in the manufacturing of ant baits in ready-to-use formulations (3g/kg) for the control of leaf-cutting ants such as the genus Atta (saúvas) and Acromyrmex (quenquéns), which are the insects that cause the most damage to agriculture. The active ingredient is effective after ingestion and presents a so called retarded action. Granulated baits represent the most widely used method for leaf-cutting ants control, consisting of a mixture of an attractive substrate (vehicle) (usually dehydrated citric pulp from the orange juice industry and vegetable oil) and an active ingredient (insecticide), presented in the form of pellets. This method seems to be low-cost that delivers high efficiency with reduced acute health hazards to humans and the environment during application, and it is specific to the pest target. Its localized application does not require application equipment. Baits are “ready to use” to be directly applied from their packaging close to active nest entrance holes or anthill trails and carried into the colony by the ants themselves. Formatted: Font: 12 pt, Font color: Text 2 Formatted: Font: 12 pt, Font color: Text 2 Best Available Technology (BAT)Alternative Chemistry for PFOS and PFOS- Comment [A33]: Updates include text copied from the Guidance document and the Technical Related Substances Paper with some slight edits. Currently, the active ingredients registered in Brazil for producing bait to control leaf-cutting Formatted: Font color: Text 2 ants are sulfluramid (in the form of granulated baits at concentrations of 0.3wt%), fenitrothion Formatted: Font color: Text 2 (to be applied via thermo-nebulization) in a mineral oil or diesel oil vehicle and deltamethrin (to Formatted: Font: Not Bold be applied in powder form) which kills on contact. Thermo-nebulization has the potential for Formatted: Font: Not Bold worker exposure and the powder form seems to be only effective in small nests. Formatted: Font: Not Bold Formatted: Font: Not Bold 24

According to the Brazilian Annex F information, sulfluramid cannot currently be efficiently Comment [A34]: Please insert reference replaced in Brazil by any other registered products commercialized for the same purpose. From the information available it is unclear which application technique and mode of action of the insecticide represents the most effective and advanced technology available. Alternative products and technologies exist and are in use. Updated information will be available after 31 October 2014 as requested in the “Call for Formatted: Normal_number, Justified information and follow-up to the sixth meeting of the Conference of the Parties to the Stockholm Convention; Number 5B”. Comment [A35]: Please insert reference Suppliers to this industry as well as users of chemicals in this industry should follow BEP practices so that emissions to the environment are minimized.

Formatted: Font color: Text 2 Best Available Technology (BAT)Alternative Chemistry for Formatted: Font color: Text 2 “Specific Exemption” Applications

Photo Masks in the Semiconductor and Liquid Crystal Display Comment [A36]: Correct title according to the (LCD) Industries Convention

Background Formatted: Font: 12 pt, Bold, Font color: Text Photomasks are an essential part of the photolithography process of semiconductor and LCD 2 production. The production process for photomasks consist of the following steps: Formatted: Font: Bold, Font color: Text 2 • Deposit a chromium layer on a glass substrate by sputtering (photomask blank) Formatted: Bulleted + Level: 1 + Aligned at: 0.25" + Indent at: 0.5" • Coat photoresist onto the chromium layer • Draw wiring pattern on the photoresist • Develop the photoresist • Remove un-covered chromium layer with etchant • Remove hardened photoresist with rinsing fluid • Dry the photomask Formatted: Font: 12 pt, Font color: Text 2 In this wet process, PFOS was used as a surfactant in the etching solution to enhance the surface Formatted: Font: 12 pt, Font color: Text 2 wettability by reducing the surface tension. This enables producing the required fine patterning Comment [A37]: Updates include text copied defect-free. from Japan’s Annex F submission in 2007. Formatted: Font color: Text 2 Best Available Technology (BAT)Alternative Chemistry for PFOS and PFOS- Formatted: Normal, Space After: 0 pt

Related Substances Formatted: Font: Not Bold PFOS was used as a surfactant in the etching solution. Formatted: Font color: Auto In most recent data (from 2007) Japan [Annex F reporting] reported estimated global use of Formatted: Font: Not Bold, Font color: Auto PFOS for this application was approximately 100kg. Formatted: Font: Bold, English (United Kingdom) Fluorinated Alternatives: No information Formatted: Normal, Space After: 0 pt Non-Fluorinated Alternatives: No information Formatted: Font: Bold, English (United Alternative Technologies: A dry process exists and is practiced for some specific cases for photo Kingdom) masks for the semiconductor industry. Formatted: Font: +Body, 11 pt, Not Bold Formatted: Font color: Auto With the exception for some specific uses, no alternative substances seem to have been Formatted: Normal, Space After: 0 pt commercialized. Therefore, PFOS represents the Best Available Technology (BAT)Chemistry as a Formatted: Font: 12 pt, Not Bold surfactant in etching solutions for photo masks. Comment [A38]: Updates include text copied from the Guidance document and the Technical Suppliers to this industry as well as users of chemicals in this industry should follow BEP Paper with some slight edits. practices so that emissions to the environment are minimized. Another resource used was: „PFOS Chromium Electroplater Study“ U.S. Environmental Protection Agency – Region 5, Sept. 2009 (http://www.epa.gov/oppt/pfoa/pubs/pfoschrome platerstudypdf_final.pdf) and from Ref. 63 Guidance Document Metal Plating (hard metal plating) Formatted: Font color: Text 2 26

Formatted: Font: 12 pt, Bold, Font color: Text Background 2 For “Background” on “Metal Plating”, please see Chapter “Metal Plating (hard metal plating) Formatted: Font: Bold, Font color: Text 2 Only in Closed-Loop Systems”. Other uses of PFOS are the alkaline zinc and zinc alloy plating, the electroless nickel dispersion coating and strong acid electrolytes with insoluble anodes, such as precious metal electrolytes (e.g. gold, palladium and rhodium). In China the following two products are being offered as potential alternatives to PFOS: • FC-53 (potassium 1,1,2,2-tetrafluoro-2-(perfluorohexyloxo)ethane sulfonate) • FC-53B (Potassium 2-(6-chloro-1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyloxy)-1,1,2,2- tetraflouroethane sulfonate) These products belong to the class of perfluorohexane sulfonyl fluorides (PFHxSF) and are related to PFHxS substances. PFHxS and related substances are considered by OECD as long- Comment [A39]: Please include reference chain perfluorinated chemicals (LCPFCs) which are not feasible as alternatives to PFOS due to from above their similar environmental hazards. Furthermore, PFHxS is regulated in the USA as part of a Comment [A40]: Please consider including: ”PFHxS has an elimination half-life in monkeys SNUR that was published in 2002. No third party assessment of the health and environmental of 141 days for males and 87 days for females impact for perfluorohexane sulfonyl fluoride (PFHxSF) and its derivatives exists. Furthermore and a geometric mean human blood elimination FC53B can only be dissolved in boiling water which makes handling much more difficult. half-life of 8.5 years (3100 days). See: S. A. Gannon et al. ”Adsorption, distribution, Therefore, FC-53 and FC-53B should not be considered as viable alternatives to PFOS. metabolism, and excretion of ([1-14C]-PFHx) in rats and mice”, Toxicology 2011. 283: p.55-62”

Comment [A41]: Need to include Federal Register Notice reference Best Available Technology (BAT)Alternative Chemistry for PFOS and PFOS- Formatted: Font: +Body, 11 pt Related Substances Formatted: Font: 12 pt, Font color: Text 2 It is important to note that the use of mist suppressants enables to meet occupational health Formatted: Font: 12 pt, Font color: Text 2 regulations and therefore each alternative needs to be assessed in those terms as well. Comment [A42]: Updates include text copied PFOS is used as a mist suppressant in hard metal plating. from the Guidance document and the Technical Paper with some slight edits. Fluorinated Alternatives: Formatted: Font color: Text 2 Formatted: Font color: Text 2 • PFBS Formatted: Font: (Default) +Body, 11 pt • 6:2 Fluorotelomer sulfonate (6:2 FTS; CAS No. 27619-97-2) Formatted: List Paragraph, Bulleted + Level: 1 Although fluorinated alternatives exist according to the Guidance on alternatives to + Aligned at: 0.25" + Indent at: 0.5" perfluorooctane sulfonate and its derivatives [referenced earlier], currently, no other surfactant Formatted: Font: (Default) +Body, 11 pt can match the low surface tension of PFOS. Therefore, the quantity required for substitution of Comment [A43]: Please include reference PFOS by polyfluorinated surfactants increases considerably about three to ten times [Reference 2 in Guidance Document]. Furthermore, the alternatives may be less stable and therefore may Comment [A44]: Please include reference have to be replenished more frequently. Non-Fluorinated Alternatives: • Alkylsulfonate (trade name: TIB Suract CR-H (TIB Chemicals AG)) Formatted: Font: (Default) +Body, 11 pt Formatted: List Paragraph, Bulleted + Level: 1 Non-fluorinated surfactants are degraded in the chromium electrolyte or etching bath and must + Aligned at: 0.25" + Indent at: 0.5" be constantly dosed. Those products are not considered equally effective. In addition, such products can reduce Cr-VI to Cr-III in the chromium electrolyte which can lead to serious faults in the chromium coating. Alternative Technology:

• PTFE coated balls on top of bath Formatted: Font: (Default) +Body, 11 pt • Mesh or blankets (Composite Mesh Pads) placed on top of bath Formatted: List Paragraph, Bulleted + Level: 1 • Add-on air pollution control devices (Packed Bed Scrubbers) + Aligned at: 0.25" + Indent at: 0.5" • Closed-Loop System (see above)

With fully capable and acceptable alternative technologies commercially available worldwide, there is no need to use PFOS, PFOS-derived, -containing or –releasing chemistry in non-closed loop hard metal plating processes. The metal plating industry has been identified as a point source of fluorinated surfactants emissions to the environment [2009 US EPA Region 5 Report]. It is important for suppliers and users in this industry to implement and adhere to Best Environmental Practices to reduce emissions to the environment.

Formatted: Font color: Text 2 Metal Plating (decorative plating) Formatted: Font: 12 pt, Bold, Font color: Text Background 2 The term “decorative” refers to a different process than described above, whereby only a thin Formatted: Font: Bold layer (0.05 to 0.5µm) of metal is deposited onto substrates. In terms of decorative chrome plating, for example, the deposited chrome layer provides the following desirable properties: • Appearance (aesthetically pleasing) • Non-tarnishing Examples of decorative chrome plated parts are: • Car and truck pumpers • Motorcycle parts • Kitchen appliances • Smart phones and tablets For further background, please see the previous chapter on hard metal plating (closed loop systems).

Formatted: Font: 12 pt, Font color: Text 2 Best Available Technology (BAT)Alternative Chemistry for PFOS and PFOS- Formatted: Font: 12 pt, Font color: Text 2 Comment [A45]: Updates include text copied Related Substances from the Guidance document and the Technical PFOS is used in this application. Paper with some slight edits. Fluorinated Alternatives: Formatted: Font color: Text 2 Formatted: Font color: Text 2 • PFBS Formatted: Font: Not Bold • 6:2 Fluorotelomer sulfonate (6:2 FTS; CAS No. 27619-97-2) Formatted: List Paragraph, Bulleted + Level: 1 Non-Fluorinated Alternatives: + Aligned at: 0.25" + Indent at: 0.5" Formatted: Font: Not Bold • Alkylsulfonate (trade name: TIB Suract CR-H (TIB Chemicals AG)) Formatted: Font: (Default) +Body, 11 pt Formatted: List Paragraph, Bulleted + Level: 1 + Aligned at: 0.25" + Indent at: 0.5" 28

Non-fluorinated surfactants are degraded in the chromium electrolyte or etching bath and must Formatted: Left, Space After: 0 pt, Don't be constantly dosed. Those products are not considered equally effective. adjust space between Latin and Asian text, Don't adjust space between Asian text and Alternative Technology: numbers Parts of the decorative chrome plating industry has adopted trivalent chromium or Cr(III) Formatted: Font: Not Bold, English (United States) plating. Cr(III) is intrinsically less toxic than Cr(VI). However, the German industry group FGKG “Fachverband Galvanisierte Kunststoffe” has recently published findings of a comparison field Comment [A46]: www.zvo.org/aktuelles/detail trial with 3000 samples. There Cr(-III) derived samples were less colour stable, more soil ansicht/artkel/fgk-zeigt-den –stand-der chrom- vi-alternativen (May 2014) sensitive and displayed higher corrosion rates. FKGK concluded that the BAT for decorative chrome plating for the automotive industry is based on Cr(-VI) plating is better suited than Cr(- III) plating.

Formatted: Font: +Body, 11 pt With a fully capable and acceptable alternative technology commercially available worldwide and in use, there is no need to use PFOS, PFOS-derived, -containing or –releasing chemistry in decorative metal plating processes. The metal plating industry has been identified as a point source of fluorinated surfactants emissions to the environment [US EPA Region 5 Report; see previous chapter]. It is important for suppliers and users in this industry to implement and adhere to Best Environmental Practices to reduce emissions to the environment.

Formatted: Font: Calibri, 11 pt, Not Bold

Electric and Electronic Parts for Some Colour Printers and Colour Copy Machines Comment [A47]: Copied from „Technical Background Paper“ An information gap exists and an assessment on Best Available TechnologyAlternative Formatted: Font: Bold, Font color: Text 2 Chemistry could not be performed due to a lack of information where exactly PFOS and/or PFOS-related substances are or have been used in the application different from the listed “Acceptable Purpose” and “Specific Exemption” applications described in this document. Formatted: Normal, Space After: 0 pt Best Available Technology (BAT)Alternative Chemistry for PFOS and PFOS- Formatted: Font: 12 pt, Font color: Text 2 Formatted: Font: 12 pt, Font color: Text 2 Related Substances Formatted: Font color: Text 2 Formatted: Normal, Space After: 0 pt Fluorinated Alternatives: No information Formatted: Font: Bold, English (United Non-Fluorinated Alternatives: No information Kingdom) Alternative Technology: No information Formatted: Font: Bold, English (United Kingdom)

Formatted: Font: Bold, English (United Kingdom) Insecticides for Control of Red Imported Fire Ants and Formatted: Font: +Body, 11 pt, Not Bold Termites Formatted: Font: 12 pt, Not Bold Formatted: Font: Bold, Font color: Text 2 Background

N-Ethyl perfluorooctane sulfonamide (EtFOSA; sulfuramid; CAS No. 4151-50-2), also called sulfluramid, is both a surfactant and a pesticide that was used against termites, cockroaches, and ants.

Formatted: Font: 12 pt, Font color: Text 2 Best Available Technology (BAT)Alternative Chemistry for PFOS and PFOS- Formatted: Font: 12 pt, Font color: Text 2

Related Substances Comment [A48]: Updates include text copied EtFOSA is no longer used to manufacture ant bait or insecticides against beetles and ants in the from the Guidance document and the Technical United States. The U.S. Environmental Protection Agency cancelled the registration of Paper with some slight edits. sulfluramid in May 2008.3 In the European Union, PFOS-related substances are not used in the Formatted: Font color: Text 2 manufacture of pesticides.4 Ant baits containing S-methoprene and pyriproxifen are registered in New Zealand for the control of exotic ants by aerial and ground applications.5 Alternative Chemistry: The reported alternatives to sulfluramid are: • Chlorpirifos • Cypermethrin • mixture of chlorpirifos and cypermethrin • fipronil • imidacloprid • abamectin • deltamethrin • fenitrothion • mixture of fenitrothion and deltamethrin. Please note, some of the alternative chemistries have been part of the “Assessment of Alternatives to endosulfan” [include reference here]. Please consider conclusions from this Comment [A49]: http://chm.pops.int/TheConv document in your selection of suitable alternatives. ention/POPsReviewCommittee/Meetings/POPR C8/MeetingDocuments/tabid/2801/Default.aspx

Alternative Technology: Comment [A50]: Insert references provided Several options have been evaluated for effectiveness: by Brazil (Alternatives Assessment 2nd draft comments) • organic bait consisting of rice grains with Beauveria sp. (De Soll et al., 2010) • Diatomaceous earth mixed with waste water in the principal entry of each anthill (Ríos de Saluso,2010) • Vegetal substances with insecticide effect: extract of eucalyptus, castor-oil plant (Pelicano et al., 2002) • “Palo Amargo” (“Bitter stick”, Aeschirium crenata Vell. Simaroubaceae) (Rodfígue et al., 2006) • Natural enemies: parasitoids known as “Moscas descapitadotas” (“Decapitating flies”, Diptera: Phoridae) (Guilllade y Folgarait, 2010) • organic baits based on yeast and rice (Borgetto, 2009)

3 www.epa.gov/fedrgstr/EPA-PEST/2008/May/Day-16/p10919.htm. 4 http://archive.defra.gov.uk/environment/quality/chemicals/documents/pfos-riskstrategy.pdf 5 Environmental Risk Management Authority of New Zealand (ERMA NZ) (2007), Decision, 2007-11-11. 30

as users of insecticides in this industry should follow BAT and BEP practices so that emissions to the environment are minimized.

Formatted: Font color: Text 2 Chemically Driven Oil Production Formatted: Font color: Text 2 Background Formatted: Font color: Text 2 It is reported that PFOS is used in some parts of the world as surfactants in oil well stimulation Formatted: Font color: Text 2 to recover oil trapped in small pores between rock particles. Oil well stimulation includes, in Formatted: Font: 12 pt, Bold, Font color: Text general, a variety of operations performed on a well to improve its productivity. The main two 2 types of operations are matrix acidization and hydraulic fracturing. Formatted: Font: Bold, Font color: Text 2

Formatted: Font: 12 pt, Font color: Text 2 Best Available Technology (BAT)Alternative Chemistry for PFOS and PFOS- Formatted: Font: 12 pt, Font color: Text 2

Related Substances Comment [A51]: Updates include text copied Fluorinated Alternatives: from the Guidance document and the Technical Paper with some slight edits. Obtaining detailed information on this use proved to be challenging. Alternatives to PFOS Formatted: Font color: Text 2 identified in two previous reports are: . PFBS . short-chain fluorotelomer-based fluorosurfactants or polymers . other perfluoroalkyl-substituted amines, acids, amino acids, and thioether acids Non-Fluorinated Alternatives: In most parts of the world where oil exploration and production are taking place, oil service companies engaged in provision of well stimulation services predominantly use formulation of alcohols, alkyl phenols, ethers, aromatic hydrocarbons, inorganic salts, methylated alcohols, for oil well stimulation. Oil well stimulation services also involve corrosion control, water blocks/blockage control, iron control, clay control, paraffin wax and asphaltene removal and prevention of fluid loss and diverting. Formatted: Font: Not Bold Alternative Technology: No information Formatted: Font: Not Bold

With fully capable and acceptable alternative technologies commercially available worldwide and in use, there is no need to use PFOS, PFOS-derived, -containing or –releasing chemistry in the chemically driven oil production industry. Suppliers to this industry as well as users of chemicals in this industry should follow BAT and BEP practices so that emissions to the environment are minimized.

Comment [A52]: This section is now separate Carpets from „Textiles“ and content has been added. References for the content have been added as well. Background Fluorinated polymers may be applied during manufacturing of residential and commercial carpets made from both synthetic and natural fibres (e.g. wool) to provide stain and soil protection. There are three scenarios for the chemical application: a) application at a carpet or rug mill during the manufacturing process; b) application to carpet after the manufacturing process at a separate finishing facility; c) re-application by professionals or end consumers in the post manufacturing stage (e.g., in offices or residences).[Reference]. Comment [A53]: “Long-Chain Perfluorinated Chemicals (LCPFCs) Used in Carpets”; Contract EP- W-08-010; Prepared for: Economic and Policy Analysis Branch; Economics, Exposure and Technology Division; Office of Pollution, Prevention Best Available Technology (BAT)Alternative Chemistry for PFOS and PFOS- and Toxics; U.S. Environmental Protection Agency; July 2012. Electronic form available at: Related Substances http://www.fluoridealert.org/wp- Fluorinated finishes are the only technology known to deliver durable stain and soil repellency. content/uploads/pfcs.carpet.report.epa_.2012.pdf Historically, fluorinated polymers based on perfluorooctane sulfonyl (PFOS-related) Formatted: Font: 12 pt, Font color: Text 2 electrochemical fluorination chemistry have been used. PFOS-related substances were used to Formatted: Font: 12 pt, Font color: Text 2 treat carpets but PFOS as such was present at up to 2wt% in articles. In addition, fluorotelomer- Comment [A54]: Text has been copied from based polymers have also been used. As stated earlier, major manufacturers in conjunction the previous original chapter as it described „chemicals for carpet treatment“. Text has been with global regulators have agreed to discontinue the manufacture of “long-chain” fluorinated slightly edited to address „Carpet“ only. products and move to “short-chain” fluorinated products. Such “short-chain” polymeric Formatted: Font color: Text 2 alternatives have entered the commercial space over the last years and have undergone much higher regulatory rigor than their “long-chain” predecessors, for example in Canada, in Europe and in the USA [for example, see ]. Comment [A55]: http://epa.gov/oppt/pfoa/pub s/altnewchems.html Fluorinated Alternatives: New short-chain-based polymeric products have been approved for manufacture, sale and use, and have been demonstrated to deliver the desired performance in textiles applications. Examples of well-known trademarked fluorinated durable water repellents are: Comment [A56]: Taken form the Guidance document – same below. One should consider 1. PFBS-based products Scotchgard™ from 3M citing the same references here as well. The references would need to be copied from the 2. Short-chain fluorotelomer-based polymeric products Guidance. a. Capstone® from DuPont Formatted b. products from Daikin and others Formatted: Font: Calibri, 11 pt Non-Fluorinated Alternative hydrophobic finishes for carpet (Water Repellency) For these applications several alternatives exist: 1. Wax-based repellents consisting of paraffin-metal salt formulations 2. Hydrophobic modified polyurethanes (hydrophobic modified hyperbranched polyurethanes called dendrimers) 3. Polysiloxane-based products 4. Resin-based repellents consisting of fatty modified melamine resins These non-fluorinated alternative technologies do not provide durable oily stain and soil repellency. If oily stain and soil repellency is required, fluorinated polymers are the state of the art. Alternative Technology for stain protected residential carpet: 32

Inherently stain-resistant (but not soil resistant) polyester carpet fibers are offered as alternative technology to soil- and stain-protected for residential use.

With fully capable and acceptable alternative technologies commercially available and in use worldwide, there is no need to use PFOS, PFOS-derived, -containing or –releasing chemistry for treating carpets. Suppliers to this industry as well as users of chemicals in this industry should follow BAT and BEP practices so that emissions to the environment are minimized.

Comment [A57]: Text was added because Leather and Apparel the application can be different from Textiles and Carpet as are the products used.

Background Fluorinated polymers may be applied during the leather making process in the tannery, in the finishing step as a surface treatment or at home by the end consumer to provide water, stain and soil protection to leather substrates such as shoes, apparel and upholstery. In the past, aqueous dispersions of anionic PFOS-related polymers have been utilized in tanneries and in consumer products such as shoe care products. Solvent-borne PFOS-related polymers have been used in the finishing process of leather as well as in consumer shoe care aerosol sprays use under the Scotchgard® brand name. This type of chemistry has been replaced by either PFBS- based polymers or by short-chain fluorotelomer-based polymers.

Formatted: Font: 12 pt, Font color: Text 2 Best Available Technology (BAT)Alternative Chemistry for PFOS and PFOS- Formatted: Font: 12 pt, Font color: Text 2 Related Substances Formatted: Font color: Text 2 Fluorinated polymers are the only technology known to deliver durable water, stain and soil repellency for leather. Historically, fluorinated polymers based on perfluorooctane sulfonyl (PFOS-related) electrochemical fluorination chemistry have been used. In addition, fluorotelomer-based polymers have also been used. As stated earlier, major manufacturers in conjunction with global regulators have agreed to discontinue the manufacture of “long-chain” fluorinated products and move to “short-chain” fluorinated products. Such “short-chain” polymeric alternatives have entered the commercial space over the last years and have undergone much higher regulatory rigor than their “long-chain” predecessors, for example in Canada, in Europe and in the USA [for example, see reference in previous chapter].

Fluorinated Alternatives: New short-chain-based fluorinated polymeric products have been approved for manufacture, sale and use, and have been demonstrated to deliver the desired performance in leather applications. Examples of such products are: • PFBS-based products: Scotchgard™ from 3M market by TFL • Short-chain fluorotelomer-based polymeric products Formatted o Nuva from Clariant Formatted: English (United States) o Products from Daikin and others Formatted: Font: Calibri, 11 pt 33

Non-Fluorinated Alternatives: Waterproofing agents (Water Repellency): These offerings exist but these do not provide oil, soil and stain protection. Some examples are: 1. Wax-based repellents consisting of paraffin-metal salt formulations 2. Hydrophobic modified polyurethanes (hydrophobic modified hyperbranched polyurethanes called dendrimers) 3. Polysiloxane-based products 4. Resin-based repellents consisting of fatty modified melamine resins

Alternative Technology: No information With fully capable and acceptable alternative technologies commercially available and in use worldwide, there is no need to use PFOS, PFOS-derived, -containing or –releasing chemistry for treating leather. Suppliers to this industry as well as users of chemicals in this industry should follow BAT and BEP practices so that emissions to the environment are minimized.

Formatted: Font: (Default) Lucida Sans Unicode, 14 pt, Font color: Auto, English (United States)

2.1 Coated and impregnated items Formatted: Indent: Left: 0.5", Hanging: 2.1.1 Introduction 0.25", No bullets or numbering, Don't adjust space between Latin and Asian text Fluorosurfactants have been used as additives in coatings for many years. For any coating to be Formatted: Font: 14 pt applied successfully, it must first wet the substrate to which it is applied. If a high gloss is Formatted: Indent: Left: 0.5", No bullets or desired, the coating must flow and level over the substrate as well. Often, the coating has a numbering, Don't adjust space between Latin higher surface tension than the substrate to be coated. This is an unfavourable situation for and Asian text proper wetting. The solution is to reduce the surface tension of the coating, which can be done Formatted: Font: Calibri, 11 pt with a variety of surfactants. Fluorosurfactants are more effective and efficient than other similar hydrocarbon surfactants in lowering the surface tensions of coatings. This means that lower surface tensions can be achieved at lower surfactant addition levels. In many coating applications, increased effectiveness and efficiency in aiding wetting are critical for the successful application of a coating. The same effectiveness and efficiency of surface tension reduction afforded by fluorosurfactants make this class of materials very useful, and often better than hydrocarbons, for providing increased flow and levelling attributes. The coatings industry is increasing production of water- borne systems to reduce volatile organic compounds (VOCs). This puts increased demand on coatings as water has a very high surface tension compared with organic coating solvents and lessens the ability to wet a substrate. Generically, coatings with lower surface tension produced by adding fluorosurfactants will function better in regard to wetting, flow and levelling.Although fluorosurfactants are typically added early in the coating formulation process, they can be added at any time. All surfactants are delivered at high concentrations and usually beyond the critical micelle concentration (cmc). Since the utility of all surfactants at wetting, flow and levelling applications is at the molecular level, rather than as aggregates, time is required to disperse. Fluorosurfactants require more time than hydrocarbon surfactants to disperse from a concentrated state. This is true particularly if R&D testing will occur soon after a test formulation is prepared.

Defoamers are often required in tandem with fluorosurfactant use. The physicochemical properties of fluorosurfactants favour long-lived, voluminous foams and particularly under the vigorous conditions used to mix coatings properly. The propensity to foam and foam lifetime are dependent on surfactant type and perfluoroalkyl chain length (“C1” ≤ “C2” < “C4” < “C6” < “C8”). Nonionic fluorosurfactants show little tendency to foam while ionics (both anionic and cationic) exhibit much more foam. Use rates of fluorosurfactants tend to follow surface tension reduction and efficiency trends. The shorter perfluoroalkyl chain fluorosurfactants, the higher addition levels they require. The fluorosurfactant level required to achieve adequate wetting, flow and levelling will depend strongly on the coating formulation. For aqueous-based coatings, the fluorosurfactant use levels required are, generally, near the cmc and range from approximately 50 ppm to 500 ppm, based on the weight of the coating. Solvent-borne coatings, however, require much higher addition levels and can range from 500 ppm to 5000 ppm, based on the weight of the coating. A typical coating application, and one of the largest consumers of fluorosurfactants, is floor polish. Every floor polish contains a fluorosurfactant. The floor polish must wet a floor that can be made of low surface tension material or contaminated with a low surface tension material. Proper wetting requires a surfactant (fluorosurfactant) that will ensure the coating has a sufficiently low surface tension to function. In addition, high gloss is very desirable with floor polish. Fluorosurfactants are excellent at mitigating surface tension gradients that can cause coating defects and reduce gloss. Any coating that has similar requirements could be formulated successfully with a fluorosurfactant. Floor polishes form a somewhat unique subset of coatings in that they are applied, removed as required for another application and then disposed directly into wastewater. This procedure differs from a typical coating, such as paint, in that environmental exposure is direct as opposed to weathering and other forms of assault by which materials can leach into the environment either as original species or degraded by oxidative, light or acidic reactions. Disposing of removed floor polish into wastewater poses environmental concerns as the techniques and chemistry involved in most municipal wastewater treatment facilities cannot process all components properly. This is true particularly for fluorosurfactants. What remains of the fluorosurfactant after treatment depends on the nature of the fluorochemical; however, degradation is often of the oxidative type and perfluorocarboxylic acids can be produced and passed to the local aquifer. As discussed above, there are PBT concerns with long perfluoroalkyl chain surfactants. In summary, environmental exposure and contamination from fluorosurfactants can be minimized or eliminated using short-chain surfactants. Ultimately, the use and choice of a particular fluorosurfactant will depend on whether the material provides the necessary performance or benefits that cannot be attained with other surfactants. The conversion from PFOS to short-chain fluorosurfactants has been considered successful to date (OECD, 2010). Formatted: Underline and alternative chemistry Formatted: Font: 12 pt, Bold PFOS It has been known for many years that the ability of a fluorosurfactant to reduce surface tension at a given concentration is superior to alternative surfactant substances (for detailed discussions of the important properties of and technology behind commercial fluorosurfactants, see Kissa 1994; Taylor 1999; Buck et al. 2011. Longer perfluoroalkyl chains ≈ lower surface tensions. Comment [A58]: Contents are used in paragraphs above.

In the years following the commercial introduction of long perfluoroalkyl chain surfactants, evidence was mounting that long chain perfluoroalkyl chain-containing materials, including fluorosurfactants, could have substantial environmental impact with regard to persistence, bioaccumulation and toxicity (PBT). The magnitude and concern of PBT of this chemical group are directly related to perfluoroalkyl chain length; they are not just caused by fluorosurfactants themselves, but also by degraded forms of chemicals. These observations have prompted a restructuring of the fluorosurfactant industry serving the coatings additives market. Large vendors (e.g. DuPont, Daikin, 3M, etc.) of long chain fluorosurfactants have discontinued, or are in the process of discontinuing, the manufacturing and marketing of fluorosurfactants in favour of short-chain alternatives. Currently, the target Formatted: Font: Calibri, 11 pt appears to be –(CF2)6F or “C6” technology. 3M has moved to a “C4” technology based on - (CF2)4F. OMNOVA Solutions has attempted to distance itself further from the mainstream with “C1” (-CF3) and “C2” (-CF2CF3)-based fluorosurfactants. Concern over PBT issues has also resulted in global regulators pressing for the phase-out of “long-chain” fluorinated substances in favour of a move to “short-chain” fluorinated substances, which are currently considered to have a more favourable overall environmental profile (OECD, 2010). Ongoing research, however, focuses on the environmental and health characteristics of the new short-chain chemistry, which is currently poorly described in recent scientific literature. Comment [A59]: Content has been summarized in the parapgraph above. Current coating processes Comment [A60]: This section has been combined with the introductory section of this Although fluorosurfactants are typically added early in the coating formulation process, they can chapter. be added at any time. All surfactants are delivered at high concentrations and usually beyond the critical micelle concentration (cmc). Since the utility of all surfactants at wetting, flow and levelling applications is at the molecular level, rather than as aggregates, time is required to disperse. Fluorosurfactants require more time than hydrocarbon surfactants to disperse from a concentrated state. This is true particularly if R&D testing will occur soon after a test formulation is prepared. Defoamers are often required in tandem with fluorosurfactant use. The physicochemical properties of fluorosurfactants favour long-lived, voluminous foams and particularly under the vigorous conditions used to mix coatings properly. The propensity to foam and foam lifetime are dependent on surfactant type and perfluoroalkyl chain length (“C1” ≤ “C2” < “C4” < “C6” < “C8”). Nonionic fluorosurfactants show little tendency to foam while ionics (both anionic and cationic) exhibit much more foam. Use rates of fluorosurfactants tend to follow surface tension reduction and efficiency trends. The shorter perfluoroalkyl chain fluorosurfactants, the higher addition levels they require. The fluorosurfactant level required to achieve adequate wetting, flow and levelling will depend strongly on the coating formulation. For aqueous-based coatings, the fluorosurfactant use levels required are, generally, near the cmc and range from approximately 50 ppm to 500 ppm, based on the weight of the coating. Solvent-borne coatings, however, require much higher addition levels and can range from 500 ppm to 5000 ppm, based on the weight of the coating. A typical coating application, and one of the largest consumers of fluorosurfactants, is floor polish. Every floor polish contains a fluorosurfactant. The floor polish must wet a floor that can be made of low surface tension material or contaminated with a low surface tension material. Proper wetting requires a surfactant (fluorosurfactant) that will ensure the coating has a sufficiently low surface tension to function. In addition, high gloss is very desirable with floor polish. Fluorosurfactants are excellent at mitigating surface tension gradients that can cause 36

coating defects and reduce gloss. Any coating that has similar requirements could be formulated successfully with a fluorosurfactant. Floor polishes form a somewhat unique subset of coatings in that they are applied, removed as required for another application and then disposed directly into wastewater. This procedure differs from a typical coating, such as paint, in that environmental exposure is direct as opposed to weathering and other forms of assault by which materials can leach into the environment either as original species or degraded by oxidative, light or acidic reactions. Disposing of removed floor polish into wastewater poses environmental concerns as the techniques and chemistry involved in most municipal wastewater treatment facilities cannot process all components properly. This is true particularly for fluorosurfactants. What remains of the fluorosurfactant after treatment depends on the nature of the fluorochemical; however, degradation is often of the oxidative type and perfluorocarboxylic acids can be produced and passed to the local aquifer. As discussed above, there are PBT concerns with long perfluoroalkyl chain surfactants. In summary, environmental exposure and contamination from fluorosurfactants can be minimized or eliminated using short-chain surfactants. Formatted: English (United States) Formatted: Normal, Left, Space After: 0 pt Ultimately, the use and choice of a particular fluorosurfactant will depend Formatted: Heading 3, Left on whether the material provides the necessary performance or benefits Comment [A61]: Leather and Paper are that cannot be attained with other surfactants. The conversion from PFOS described in subsequent chapters to short-chain fluorosurfactants has been considered successful to date Edits include text from the Guidance Document (OECD, 2010). and the Technical Paper. Formatted: No bullets or numbering, Don't adjust space between Latin and Asian text Formatted: Font: (Default) Lucida Sans Unicode, 14 pt, Bold Formatted: Font: (Default) Lucida Sans Textiles and Upholstery Unicode, 14 pt, Bold Formatted: Font: (Default) Lucida Sans 2.1.2 , paper and leather Unicode, 14 pt, Bold Background Fluorosurfactants Side-chain fluorinated polymers [include reference] are used by Formatted: Font: 12 pt, Bold the textile industry for the treatment of all-weather clothing, umbrellas, bags, sails, tents, Comment [A62]: Please include the following references: ”Synthesis Paper on Per- and parasols, sunshades, upholstery, footwear, rugs, mats, and the like to repel water, oil and dirt Polyfluorinated Chemicals (PFCs)”, OECD/UNEP (stains) without imparing the breathability (air and water vapour permeability) of the fabric. Global PFC Group, June 2013; http://www.oecd.org/env/ehs/risk- management/PFC_FINAL-Web.pdf And Buck, R. C.; Franklin, J.; Berger, U.; Conder, J. M.; Cousins, I. T.; De Voogt, P.; Jensen, A. A.; Kannan, K.; Mabury, S. A.; van Leeuwen, S. P. J. Perfluoroalkyl and polyfluoroalkyl substances in the environment: terminology, classification, and origins. Integr Environ Assess Manag 2011, 7, 513–541; Open Access Publication: http://onlinelibrary.wiley.com/doi/10.1002/ieam.25 8/full Formatted: No bullets or numbering, Tab stops: 2.83", Left Formatted: Font: +Body, 11 pt Formatted: Font: +Body, 11 pt Formatted: Font: +Body, 11 pt Formatted: Font: +Body, 11 pt 37

and polymers have been used to treat textiles and leather to provide oil and water repellence and soil and stain release properties, and to provide oil, grease and water repellence for paper. Fluorinated polymers are used to render textiles stain- and waterproof when required, but they also have to keep their breathability (air and water-vapour permeability). They are mainly applied to home textiles like upholstery and to outdoor wear, especially work wear including uniforms and shoes. The earliest applications used fluorosurfactants. These were quickly replaced, however, with high molecular weight fluorinated polymers, most commonly either PFOS-related or fluorinated poly(meth)acrylates based on fluorotelomer chemistry, also denoted as side-chain fluorinated polymers. The side-chain fluorinated polymers are typically aqueous polymer dispersions that are diluted and then applied to the textile, leather or paper, and then dried on at a textile mill or industrial contract finisher. The polymers are designed to strongly adsorb and, in some cases, chemically bond to theany kind of textile fiber textile, leather or paper. For textiles and leather, theThe polymers are designed to perform after multiple cleanings/washings and last the lifetime of the treated article.

Finishing processes Comment [A63]: This chapter will be considered later on in the BEP Section Generally, finishing operations can be divided into a variety of mechanical finishing processes by applying a surface coat or through impregnation of a surface of paper, textile, leather or some other material. The overall objective of finishing is to enhance the appearance of the finished product and to provide the performance characteristics expected of the finished product with respect to colour, gloss, handle, flex, adhesion, and rub fastness; as well as other properties including extensibility, break, light- and perspiration fastness, water vapour permeability and water resistance as required for the end use. A wide range of mechanical finishing operations may be carried out to improve the appearance and feel of the finished articles (IPPC , 2003). The purpose of applying a surface coat is to provide: • Protection from contaminants (water, oil, soiling, etc.) • Colour to modify dyed colour, reinforce colour provided by the dyes, even the colour or disguise defects • Modifications to handle and gloss performance • Attractive fashion or fancy effects • Modifications to meet other customer requirements Current coating and printing processes These processes involve the application of a thin film or paste of a functional material ― in this case a fluorchemical product ― to materials such as paper, fabric, film, foil or sheet stock. There are various coating techniques on the market, including: • Gravure coating • Reverse roll coating • Knife over roll coating "gap coating" • Metering rod coating • Slot die (Slot, Extrusion) coating • Immersion (Dip) coating • Curtain coating • Air knife coating

Current impregnation processes Fluorochemical repellents are usually applied in combination with other finishing auxiliaries by a pad-dry-cure process, as shown in figure 2-1.

Formatted: Font: Calibri, 11 pt

Figure 2-1: General principle for the pad dry cure process (IPPC, 2003) Note: Baking is sometimes called curing or fixation.

In many cases they are applied with “extenders”, which can be other repellents themselves (e.g. melamine resins repellents or polyisocyanates). The use of these "extenders" allows a reduction in the required amount of fluorochemical, with a corresponding reduction in costs for this treatment. Finishing treatments with fluorochemical repellents produce emissions of VOCs in exhaust air. These emissions are attributable to the following: • The solvents contained in the formulations (ketones, esters, alcohols, and diols). • The “extenders”, which under high-temperature conditions give rise to cracked by- products such as alcohols and ketones, but also oximes and in particular butanoxime (which is carcinogenic). • The organofluoro components, which also release cracked fluororganic by-products. Formatted: Justified, Indent: Left: 0.5" With respect to water pollution, it has to be taken into account that polysiloxanes, melamine and fluorocarbon resins are all characterized by poor biodegradability and bioeliminability (IPPC, Comment [A64]: Polymers usually do not bioaccumulate. The polymers are stabke and 2003). do not biodegrade easily.

Formatted: Font: 12 pt, Bold, Not Italic Best Available Technology (BAT)Alternative Chemistry for PFOS and PFOS-Related Substances Formatted: Font: 12 pt, Bold, Not Italic Textiles, paper and leather chemistry Formatted: Font: Bold, Not Italic PFOS and alternative chemistry Fluorinated finishes are the only technology known to deliver durable and effective oil and water repellence and release properties. Historically, fluorinated polymers based on perfluorooctane sulfonyl (PFOS-basedrelated) electrochemical fluorination chemistry have been used. PFOS-related substances were used to treat textiles but PFOS as such was present at up to 2 wt % in articles. In addition, fluorotelomer-based polymers have also been used. As stated earlier, Mmajor manufacturers, in conjunction with global regulators, have agreed to discontinue the manufacture of “long-chain” fluorinated polymeric products and move to “short-chain” fluorinated polymeric products. Such “short-chain” polymeric alternatives have entered the commercial space over the last years and have undergone much higher regulatory rigor than their “long-chain” predecessors, for example in Canada, in Europe and in the USA [for example, see reference in previous chapter].

Fluorinated Alternatives: Formatted: List Paragraph, Numbered + . New short-chain-based polymeric products, currently defined as BAT to achieve the needed Level: 1 + Numbering Style: 1, 2, 3, … + Start performance effects, have been approved for manufacture, sale and use, and have been at: 1 + Alignment: Left + Aligned at: 0.25" + Indent at: 0.5" demonstrated to deliver the desired performance in textiles, leather and paper applications. Examples of well-known trademarked fluorinated durable water repellents are: Formatted: Font: Calibri, 11 pt Formatted: List Paragraph, Numbered + 1. PFBS-based products: Scotchgard™ from 3M Level: 2 + Numbering Style: a, b, c, … + Start 2. Short-chain fluorotelomer-based polymeric products at: 1 + Alignment: Left + Aligned at: 0.75" + Indent at: 1" a. Products from Archroma (formerly Clariant) Formatted: Font: Calibri, 11 pt b. Products from Asahi Glass c. Products from Daikin Formatted: List Paragraph, Numbered + Level: 2 + Numbering Style: a, b, c, … + Start d. Capstone® from DuPont at: 1 + Alignment: Left + Aligned at: 0.75" + e. Products from Rudolf Chemie and others Indent at: 1" Formatted: Font: Calibri, 11 pt 40

3. Fluorinated oxetane-based products: Omnova Formatted: Font: Calibri, 11 pt Formatted: List Paragraph, Numbered + Level: 1 + Numbering Style: 1, 2, 3, … + Start Non-Fluorinated Alternatives: hydrophobic finishes for textiles at: 1 + Alignment: Left + Aligned at: 0.25" + Water Repellency: Indent at: 0.5" Non-fluorinated alternatives technologies such as hydrocarbon waxes and silicones can provide durable water repellence (DWR; aka hydrophobic properties) but not oil repellence or oil and soil release. If oil, stain, blood or soil repellence is required, fluorinated polymers are the state of the art. . For most of the applications, such as outdoor clothing, tents, awnings etc., the durable water- repellent effect (DWR) of the fabric is might be the main property requested by the users. For these applications, there are several existing alternatives exist: to fluorocarbons that are not based on persistent molecules:

1. • Wax-based repellents consisting of paraffin-metal salt formulations Formatted: Numbered + Level: 1 + Numbering Style: 1, 2, 3, … + Start at: 1 + 2. • Hydrophobic modified polyurethanes (hydrophobic modified hyperbranched Alignment: Left + Aligned at: 0.25" + Indent polyurethanes called dendrimers; Bionic Finish Eco® from Rudolf Chemie) at: 0.5" 3. • Silicone repellents 4. • Resin-based repellents consisting of fatty modified melamine resins Non-fluorinated alternative technologies such as hydrocarbon waxes and silicones can provide durable water repellence (DWR; aka hydrophobic properties) but not oil repellence or oil and soil release. If oil, blood or soil repellence is required, fluorinated polymers are the state of the art.

Alternative technology: No information With fully capable and acceptable alternative technologies commercially available and in use worldwide, there is no need to use PFOS, PFOS-derived, -containing or -–releasing chemistry in treating textiles, leather or paper. Suppliers to this industry as well as users of chemicals in this industry should follow BAT and BEP practices so that emissions to the environment are minimized. Since these alternatives have their own special profiles, the textile industry needs to be very selective about BAT and BEP depending on for which purpose which kind of chemistry is used.

Comment [A65]: This section is now separate 2.1.3 Carpets from „Textiles“ and content has been added. References for the content have been added as Fluorinated polymers may be applied during manufacturing of carpets made from both synthetic well. and natural fibres (e.g. wool) to provide stain and soil protection. Of paramount importance is Formatted: No bullets or numbering, Don't the ability to repel oily soil. The products are typically aqueous dispersions of fluorinated adjust space between Latin and Asian text polymers that are applied to the surface of a carpet by either spraying or applying by foam Formatted: Font: (Default) Lucida Sans application an aqueous solution of the fluorinated polymer immediately followed by drying. The Unicode, 14 pt, Bold fluorinated polymer is designed to adhere strongly to the carpet fibres and withstand abrasive Formatted: Font: (Default) Lucida Sans Unicode, 14 pt, Bold wear and cleaning. The situation regarding past and current chemistry is the same for carpets as described for textiles, leather and paper (see section 2.1.2). Since there are fully capable and acceptable

alternative technologies commercially available worldwide, there is no need to use PFOS- Comment [A66]: Replaced by paragraph derived, -containing or -releasing chemistry in treating carpets. above. Formatted: Normal, No bullets or numbering 2.1.4 Comment [A67]: Updates include text copied Paper and packagingPackaging form the Guidance document and the Technical Paper with some slight edits. Background Formatted: Font: 14 pt, Bold Formatted: Font: 14 pt, Bold Fluorinated compounds are used to render paper, and cardboard and molded pulp articles grease- and waterproof and are thus applied only in a small part of the overall paper market Formatted: No bullets or numbering, Don't adjust space between Latin and Asian text (approximately 8%), targeted towards specialty papers for which grease protection is necessary. Formatted: Font: 14 pt, Bold Such types of coated papers are of special importance in the food industry. Some examples are: Formatted ... Formatted: Font: Bold, Font color: Text 2 Food contact applications such as plates (molded pulp), food containers, (microwave) popcorn Formatted: Font: +Body bags, pizza boxes, fast food wraps and pet food packaging. Please note, specific regulations exist in many countries that regulate and approve products for use in food contact applications. Formatted: Font: +Body, 11 pt Formatted: Font: +Body, 11 pt

Formatted: Font: +Body, 11 pt Non-food contact applications such as folding cartons, containers, carbonless copy forms and Formatted: Font: +Body paint masking papers. Formatted: Font: +Body, 11 pt Similar to carpets, textiles and leather, PFOS itself is not directly applied but is part of a polymer. Formatted: Font: +Body, 11 pt Again, some PFOS remains as impurity in the polymer, which gives rise to the residual PFOS Formatted: Font: +Body, 11 pt content, typically in the range of 1% (Kara et al., 2010). Fluorinated surfactants have been Formatted: Font: +Body, 11 pt evaluated for paper uses since the early 1960s . Perfluorooctyl sulfoamido ethanol-based Formatted: Font: +Body, 11 pt phosphates were the first substances used to provide grease repellence to food contact papers. Formatted: Font: +Body, 11 pt Fluorotelomer thiol-based phosphates and polymers followed. Those were then followed by polyfluoroalkyl phosphonic acids (PAPs) in food contact paper products. Since paper fibers and Formatted: Font: +Body, 11 pt phosphate-based fluorinated surfactants are both anionic, cationic bridge molecules need to be Formatted: Font: +Body, 11 pt used in order to ensure the electrostatic adsorption of the surfactant onto the paper fiber. Formatted: Font: +Body, 11 pt In terms of oil and water repellency, it is well recognized in the paper industry that phosphate- Formatted: Font: +Body, 11 pt based fluorinated surfactants provide good oil repellency but have limited water repellency. Formatted: Font: +Body, 11 pt Acrylate polymers with fluorinated side chains derived from sulfoamido alcohols and Formatted ... fluorotelomer alcohols have been the most widely used polymers because they deliver oil, Comment [A68]: Please include reference grease, and water repellence. Most recently, perfluoropolyether-based phosphates and Formatted: Font: +Body polymers have become widely used treatments for food contact paper and paper packaging [6 – reference from Technical Paper]. Formatted ... Formatted ... Formatted ... Best Available Technology (BAT)Alternative Chemistry for PFOS and Comment [A69]: Updates include text copied ... PFOS-Related Substances Formatted ... In the past, paper protection by PFOS derivatives has been achieved by using one Formatted ... of the following: Formatted ... Formatted: Font: +Body, 11 pt, Not Bold Mono-, di- or triphosphate esters of N-ethyl perfluorooctane sulfonamidoethanol (EtFOSE) Formatted ... Formatted: Font: +Body, 11 pt, Not Bold N-Methyl perfluorooctane sulfonamidoethanol acrylate polymers. Formatted: Font: +Body, 11 pt, Not Bold Formatted: Font: +Body, 11 pt 42

Major manufacturers, in conjunction with global regulators, have agreed to discontinue the manufacture of “long-chain” fluorinated polymeric products and move to “short-chain” fluorinated polymeric products. Such “short-chain” polymeric alternatives have entered the commercial space over the last years and have undergone much higher regulatory rigor than their “long-chain” predecessors, for example in Canada, in Europe and in the USA [for example, see reference in previous chapter]. As stated in section 2.1.2, there is no need to use PFOS-derived, -containing or -releasing chemistry in treating paper. There are fully capable and acceptable alternative technologies commercially available worldwide. Fluorinated Alternatives: Formatted: Font: +Body, Bold The paper industry is using 1.0-1.5wt% (based on dry weight of fibres) short-chain Formatted: Font: Not Bold fluorinated polymers to produce waterproof and greaseproof paper, cardboard and molded Formatted: No bullets or numbering pulp articles. Following are the main suppliers of fluorinated polymers in the paper industry, Formatted: Font: Not Bold with their brand names (in alphabetical order): Formatted: Font: +Body, 11 pt, Not Bold • Short-chain fluorinated telomer-based polymers: Formatted: Font: +Body, 11 pt, Not Bold Formatted: Font: +Body, 11 pt, Not Bold o Archroma Paper (Formerly Clariant Paper) Cartafluor Formatted: Bulleted + Level: 1 + Aligned at: o Asahi Asahigard® 0.25" + Indent at: 0.5" Formatted: English (United Kingdom) o Ashland ImPress® Formatted: Bulleted + Level: 2 + Aligned at: o Daikin Unidyne® 0.75" + Indent at: 1" Formatted: Font: +Body, 11 pt o DuPont Capstone® Formatted: Font: +Body, 11 pt Rudolf Chemie Ruco-guard® o Formatted: Font: +Body, 11 pt • Fluoro-polyethers: Formatted: Font: +Body, 11 pt o Solvay Solvera® Formatted: Font: +Body, 11 pt Formatted: Font color: Auto Non-Fluorinated Alternatives: Formatted: Font: +Body, 11 pt Non-fluorinated alternatives cannot achieve the stringent performance requirements for oil and Formatted: Font: +Body, 11 pt grease resistance but can achieve excellent water repellency. Formatted: Bulleted + Level: 1 + Aligned at: 0.25" + Indent at: 0.5" Alternative Technology: Formatted: Font: +Body, 11 pt At least one manufacturer has developed a non-chemical alternative for this use. The Norwegian Formatted: Bulleted + Level: 2 + Aligned at: paper producer Nordic Paper is using mechanical processes to produce, without using any 0.75" + Indent at: 1" persistent chemical, extra-dense paper that inhibits leakage of grease through the paper. [2 – Formatted: Font: +Body, 11 pt reference from Technical Paper] Formatted: Font: Bold Formatted: Normal, Don't adjust space between Latin and Asian text, Don't adjust With fully capable and acceptable alternative technologies commercially available and in use space between Asian text and numbers worldwide, there is no need to use PFOS, PFOS-derived, -containing or –releasing chemistry in Formatted: Font: Bold treating paper, cardboard and molded pulp. Suppliers to this industry as well as users of Comment [A70]: Please include reference chemicals in this industry should follow BAT and BEP practices so that emissions to the environment are minimized.

Comment [A71]: Section has been edited Coatings and Coating Additives with original content and content from Guidance document and Technical Paper and has been Background shortened. Coatings: Formatted: Font color: Text 2 In the past, PFOS-related fluorinated polymers containing up to 4% of fluorinated residuals were Formatted: Font: 12 pt, Bold, Font color: Text 2 sold as coating materials for e.g. printed circuit boards and hard disk drive components. Such coatings provide protection against corrosion, contamination and grime as well as repellency Formatted: Font: Bold, Font color: Text 2 properties leading to an improved manufacturing efficiency. Formatted: Font color: Auto Coating Additives: Fluorinated surfactants provide exceptional wetting, leveling and flow control for water-based, solvent-based and high-solids organic polymer coating systems when added in amounts of just 100–500ppm. These properties result in: • improved anti-crater and improved surface appearance • better flow and levelling • reduced foaming • decreased block • extended open-time • increased bond strength • oil repellency • dirt pick-up resistance Typical industries utilizing fluorinated surfactants to achieve these properties include: • industrial and institutional floor polishes • architectural paints and coatings • varnishes • printing inks • adhesives Formatted: Indent: Left: 0.5", No bullets or For detailed discussions of the important properties of and technology behind commercial numbering fluorosurfactants, see Kissa 1994; Taylor 1999; Buck et al. 2011. Comment [A72]: Please include these One of the largest consumers of PFOS and PFOS-related fluorosurfactants, was floor polish for references industrial and institutional flooring. The floor polish must wet a floor that can be made of low surface energy material or that may be contaminated with a low surface tension (hydrophobic) material. Proper surface wetting requires a surfactant that will ensure the coating has a sufficiently low surface tension to function. In addition, high gloss is very desirable with floor polish. Fluorosurfactants are excellent at mitigating surface tension gradients that can cause coating defects and reduce gloss. Floor polishes form a somewhat unique subset of coatings in that they are applied and removed as required for another floor care application and then disposed directly into wastewater. Disposing of removed floor polish into wastewater poses environmental concerns as the techniques and chemistry involved in most municipal wastewater treatment facilities cannot process all components properly. This is true particularly for fluorosurfactants. What remains of the fluorosurfactant after treatment depends on the nature of the fluorosurfactant; however, degradation is often of the oxidative type and perfluorocarboxylic acids can be produced and passed to the local aquifer.

Ultimately, the use and choice of a particular fluorosurfactant will depend on whether the Formatted: Font: +Body, 11 pt material provides the necessary performance or benefits that cannot be attained with other surfactants. In the past PFOS has been used in the described applications. The conversion from PFOS to short-chain fluorosurfactants has been considered successful to date (OECD, 2010). Comment [A73]: Please include this referecne Formatted: Font: +Body, 11 pt Best Available Technology (BAT)Alternative Chemistry for PFOS and

PFOS-Related Substances Major manufacturers, in conjunction with global regulators, have agreed to discontinue the manufacture of “long-chain” fluorinated polymeric products and move to “short-chain” fluorinated polymeric products. Such “short-chain” polymeric alternatives have entered the commercial space over the last years and have undergone much higher regulatory rigor than their “long-chain” predecessors, for example in Canada, in Europe and in the USA [for example, see reference in previous chapter]. Use rates of fluorosurfactants tend to follow surface tension reduction and efficiency trends. The shorter perfluoroalkyl chain fluorosurfactants, the higher addition levels they require. The fluorosurfactant level required to achieve adequate wetting, flow and levelling will depend strongly on the coating formulation as well. For aqueous-based coatings, the fluorosurfactant use levels required are, generally, near the cmc and range from approximately 50 ppm to 500 ppm, based on the weight of the coating. Solvent-borne coatings, however, require much higher addition levels and can range from 500 ppm to 5000 ppm, based on the weight of the coating.

For Coatings: Fluorinated Alternatives: • Perfluorobutance sulfonate (PFBS)-based polymers (e.g. Novec® products from 3M) Non-Fluorinated Alternatives: No information Alternative Technology: No information

For Coating Additives:

Fluorinated Alternatives: Comment [A74]: Taken from the Guidance Document and the Technical Paper 1. Short chain fluorotelomer-based surfactants6 (e.g., Capstone® products from DuPont); 2. Perfluorobutane sulfonate (PFBS)-based compounds (e.g., Novec® products from 3M) 3. Fluorinated polyethers (e.g., PolyFox® products from Omnova) Non-Fluorinated Alternatives:

6 Perfluorocarboxylic Acid Content in 116 Articles of Commerce, US EPA (2009) http://www.oecd.org/env/48125746.pdf.

1. Sulfosuccinates, for example the sodium salt of di-(2-ethylhexyl) sulfosuccinate dissolved in ethanol and water, which is used as an alternative in wood primers and printing inks 2. Silicone polymers, such as polyether-modified polydimethyl siloxane, mixed with di-(2-ethylhexyl) sulfosuccinate in ethanol and water (WorléeAdd®) 3. Propylated naphthalenes and propylated biphenyls, which can be used as water repelling agents for applications such as rust protection systems, marine paints, resins, printing inks and coatings in electrical applications 4. Fatty alcohol polyglycol ether telomers, sometimes together with a sulfosuccinate Alternative Technology: No information With fully capable and acceptable alternative technologies commercially available and in use worldwide, there is no need to use PFOS, PFOS-derived, -containing or –releasing fluorinated surfactants as coating additives or for coatings. Suppliers to this industry as well as users of chemicals in this industry should follow BAT and BEP practices so that emissions to the environment are minimized.

Rubber and Plastics Background PFOS and/or PFOS-related substances have been used as mold release agents in rubber and plastics moulding applications.

Best Available Technology (BAT)Alternative Chemistry for PFOS and PFOS- Comment [A75]: Updates include text copied Related Substances from the Guidance document and the Technical Fluorinated Alternatives: Paper with some slight edits. Perfluorobutane sulphonate (PFBS) derivatives or various C4-perfluorocompounds Non-Fluorinated Alternatives: No information Alternative Technology: No information With fully capable and acceptable alternative technologies commercially available worldwide, and in use there is no need to use PFOS, PFOS-derived, -containing or –releasing chemistry in the rubber and plastics industry. Suppliers to this industry as well as users of chemicals in this industry should follow BAT and BEP practices so that emissions to the environment are minimized.

Insecticides Formatted: No bullets or numbering, Don't 2.2 adjust space between Latin and Asian text 2.2.1 Introduction Formatted: Font: 14 pt Sulfluramid is the only active ingredient with all the properties necessary for effective functioning as ant bait, which makes it the only effective option for controlling leaf-cutting ants.

N-Ethyl perfluorooctane sulfonamide (EtFOSA; sulfluramid; CAS No. 4151-50-2), also called sulfluramid, is both a surfactant and a pesticide used against termites, cockroaches, and ants. In addition to their function as pesticides, fluorosurfactants may be used as “inert” surfactants (enhancers) in pesticide products. The two PFOS-related substances, potassium N-ethyl-N- [(heptadecafluorooctyl) sulfonyl] glycinate (CAS No. 2991-51-7) and 3- [[(heptadecafluorooctyl)sulfonyl]amino]-N,N,N-trimethyl 1-propanaminium iodide (CAS No. 1652-63-7), have been approved in pesticide formulations in the United States (US). Both chemicals have other uses, for example as cleaning agents. PFOS derivatives were used in pesticides because they were considered rather inert and non-toxic to humans. Comment [A76]: This information is not relevant for this document and should be 2.2.2 Current removed. insecticides for control of red imported fire Formatted: No bullets or numbering, Don't ants and termites adjust space between Latin and Asian text N-Ethyl perfluorooctane sulfonamide (EtFOSA; sulfluramid; CAS No. 4151-50-2), also called Formatted: Font: 14 pt, Bold sulfluramid, is both a surfactant and a pesticide used against termites, cockroaches, and ants. Sulfluramid is a PFOS-related substance that was used in insecticides at a concentration of 0.01- 0.1% at an annual volume of up to 17 tonnes (OECD, 2006). According to information submitted to the Secretariat of the Stockholm Convention, sulfluramid is used for pest control (to control cockroaches, white ants, and fire ants) in China (UNEP/POPS/POPRC.6/13/Add.3, 2010). Comment [A77]: This information is not relevant for this document and should be 2.2.3 PFOS-related substances and alternative pesticides for the control removed. of leaf-cutting ants Formatted: No bullets or numbering, Don't adjust space between Latin and Asian text Sulfluramid is still used in Brazil as an active ingredient in the manufacturing of ant baits for the control of leaf-cutting ants belonging to the genus Atta (saúvas) and Acromyrmex (quenquéns), which are the insects that cause the most damage to the agriculture sector of the country: Currently, the active ingredients registered in Brazil for producing baits to control leaf-cutting ants are sulfluramid, fipronil and chlorpyrifos. The latter two, however, are considered more acutely toxic to humans and the environment than sulfluramid. Furthermore, the effectiveness of these substances has been questioned; thus new alternatives are being studied in Brazil. In sulfluramid cannot currently be efficiently replaced in Brazil by any other registered products commercialized for the same purpose. Sulfluramid is the only active ingredient with all the Comment [A78]: The same information is properties necessary for effective functioning as ant bait, which makes it the only effective used in the beginning of this paragraph and should therefore be deleted here. option for controlling leaf-cutting ants. There are many differences between leaf-cutting ants and exotic ants (urban ants), including in alimentary behaviour. Such differences explain why certain active ingredients are effective for controlling urban ants and not for controlling leaf-cutting ants. Fenoxycarb, pyriproxyfen, diflubenzuron, teflubenzuron, silaneafone, thidiazuron, tefluron, prodrone and methoprene had been tested for leaf-cutting ants, but they were not effective. An adequate insecticide used to formulate baits for the control of leaf-cutting ants should be lethal at low concentrations, act by ingestion and present a delayed toxic action. Since 1958, over 7,500 chemical compounds for ant control have been studied in many countries. Less than 1% of those 7,500 compounds have shown promise. (UNEP/POPS/POPRC.6/13/Add.3, 2010) Comment [A79]: Since no alternatives to control leaf-cutting ants seem to exist, this information is not relevant to this report and should be removed.

Aviation hydraulic fluids Comment [A80]: Updates include text copied 2.3 from the Guidance document and the Technical Paper with some slight edits. 2.3.1 PFOS and alternative chemistry Formatted: Font: 14 pt In the manufacturing process of aviation hydraulic fluids, PFOS-related substances or precursors, Formatted: No bullets or numbering, Don't such as potassium perfluorooctane sulphonate, were used as an additive, with a content of adjust space between Latin and Asian text about 0.1% (UNEP/POPS/POPRC.6/13/Add.3, 2010), to prevent evaporation, fires, and corrosion. Formatted: Font: 14 pt There is uncertainty about alternative substances in this area. Aviation hydraulic fluids without Formatted: Font: 14 pt fluorinated chemicals but based on, for example phosphate esters, exist, and fluorinated chemicals other than PFOS can be used. A search for alternatives is said to have been going on for the past 30 years. While several different compounds are said to have been tested, neither the fluorotelomers nor the non-fluorinated chemicals have met the performance requirements or the high safety standards of this industry. The potassium salt of perfluoroethylcyclohexyl sulphonate (CAS No. 67584-42-3) is not a PFOS precursor, and has been used in hydraulic oils instead of PFOS. 3M, however, which formerly produced this chemical, has ceased to do so, probably because of lack of demand (UNEP/POPS/POPRC.6/13/Add.3, 2010).

Fire fighting foams Formatted: No bullets or numbering, Don't 2.4 adjust space between Latin and Asian text 2.4.1 Finishing processes Formatted: Font: 14 pt

Aqueous film-forming foam (AFFF), sometimes referred to as aqueous fire fighting foam, is a generic term for fire fighting and/or vapour suppression products used globally to protect both lives and property. AFFFs are unique among other fire fighting foams in that they contain a small percentage of fluorinated surfactant (fluorosurfactant). This key ingredient brings unique performance attributes to the product, which enable it to be extremely effective in preventing and extinguishing fires, especially Class B flammable liquid events. AFFF products can be used in fixed and portable systems (e.g. sprinkler systems, handheld fire extinguishers, portable cylinders, fire fighting vehicles (fire trucks), etc.). In most situations, AFFF is purchased as a concentrate, typically referred to as “3%” or “6%” depending on its mixture ratio (during use) with water. Not every situation will necessarily require the use of fire fighting foams. Selection of the correct product can only be determined by a careful consideration of the specific situation at hand (emergency incident or design of life/property protection system) and review of local building codes and other regulations. It is important to remember that foams have proven to be highly effective for their intended purpose. 2.4.2 Types of foams Formatted: No bullets or numbering, Don't adjust space between Latin and Asian text Foams have been developed for both Class A (solid combustibles) and Class B (flammable liquids) fires. AFFFs were designed to be especially effective in dealing with Class B incidents. Class B foams have two major categories: synthetic foams and protein foams. Synthetic foams

AFFFs and alcohol-resistant AFFFs (AR-AFFFs) are synthetic foams based on synthetic (but not fluorochemical) surfactants. AR-AFFFs are designed to be effective in the presence of alcohols and other water miscible compounds. Protein foams Protein foams contain natural proteins as foaming agents and, as such, are not more or less biodegradable than synthetic foams. Types of protein foams include regular protein foam (P), fluoroprotein foam (FP), film-forming fluoroprotein foam (FFFP), alcohol-resistant fluoroprotein foam (AR-FP), and alcohol-resistant film-forming fluoroprotein (AR-FFFP). The chemicals used to make the fluorosurfactants that are a key ingredient in AFFF have been manufactured by different processes and have different chemical structures. Prior to 2000, fluorosurfactants used in AFFFs were often PFOS-based, which resulted in AFFFs that contained PFOS or PFOS precursors. At the same time, AFFFs based on long-chain fluorotelomers were also available for certain products and uses. Shortly after the manufacturing phase-out announcement by 3M of PFOS-based products in 2000, PFOS-based AFFFs were generally no longer available within developed countries. The primary supply of AFFF then became fluorotelomer-based. Over the last several years, manufacturers of fluorotelomer AFFF have been replacing long-chain fluorosurfactants with shorter-chain fluorosurfactants. The perfluorinated compounds (PFCs) in current fluorotelomer-based AFFF are shorter-chain molecules, generally 6:2 telomer-based, and tend to be less bioaccumulative and less toxic. Telomer-based AFFF does not contain PFOS but may contain constituents that can be degraded to PFOA or shorter-chain perfluorinated carboxylic acids. 2.4.3 Choosing an AFFF Formatted: No bullets or numbering, Don't adjust space between Latin and Asian text The choice of foam to be used in any specific situation needs to be carefully made, taking into consideration numerous factors. Fire protection experts clearly need to have a lead role in making these decisions. When evaluating foam for use in preventing or fighting a fire, several factors could be considered: • Is any type of foam actually needed? For example, in a Class A incident, it may not be necessary to use any foam to control the situation. • If use of a foam is deemed appropriate and/or necessary, does it need to be a Class B foam? While Class B foams may be quite effective on Class A fires, other techniques may be equally effective and more appropriate. • If a Class B (flammable liquids) situation presents itself, which type of Class B foam would be most appropriate and most effective? • For situations calling for the use of AFFF or AR-AFFF, has consideration been given to using the latest products available on the market? This question may also surface as the inventory of existing AFFF ages and routine performance evaluations may point to the need to replace a product.

One reference that identifies alternatives for use can be found in the “Guidance on Alternatives to Perfluorooctane Sulphonate and its Derivatives (UNEP/POPS/POPRC.6/Add.3, 2010). As stated previously, it is critically important that the tremendous effectiveness of AFFF products in protecting life and property be considered in making use and system design decisions. The expertise of fire protection personnel is imperative in such matters.

Formatted: No bullets or numbering, Don't 2.5 Decorative and hard metal plating processes adjust space between Latin and Asian text 2.5.1 PFOS and alternative chemistry

PFOS is useful as a surfactant or wetting agent in the electroplating industry to achieve uniform thickness of the plating or uniform chemical attack (Zhou et al., 2003). It also serves as a mist- suppressing agent so as not to contaminate nearby baths and to reduce the losses by drag-out (UNEP/POPS/POPRC.3/20/Add.5, 2007). In chrome plating it decreases aerosol emissions and improves the work environment. PFOS was previously used for decorative chrome plating, but new technology using chromium-III instead of chromium-VI has made this use mostly obsolete. Although the use of chromium-III does not work for hard chrome plating, some kinds of non-PFOS agents are being used in both decorative and hard chrome plating. Non-fluorinated alternatives for decorative chromium plating and hard chromium are available on the European market. They are quite new, and some are still being tested. These biodegradable alternatives seem to work, but require continually adding to and stirring the chromium bath along with some technical changes before these substitutes can be used. In the meantime telomer-based surfactants, too, are used as a bridge technology. 2.5.2 Electroplating of plastics Formatted: No bullets or numbering, Don't adjust space between Latin and Asian text PFOS is used as a wetting agent in the pre-treatment (etching) of plastics, which is essential before the electroplating process. It provides the wettability of the surface and uniform chemical attack of the chromic and sulphuric acid used for etching.

2.5.3 Rubber and plastic products Formatted: Font: 14 pt, Bold, Font color: Text 2 Perfluorobutane sulphonate (PFBS) derivatives or various C4-perfluorocompounds are used as Formatted: Normal, Space After: 0 pt, No alternatives to PFOS in rubber moulding defoamers in electroplating and as additives in plastics. bullets or numbering More information on alternatives to PFOS can be found in the “Guidance on Alternatives to Formatted: Font: (Default) Lucida Sans Perfluorooctane Sulphonate and its Derivatives (UNEP/POPS/POPRC.6/13/Add.3, 2010). Unicode, Bold, Font color: Text 2 Formatted: Font: Calibri, 11 pt Formatted: Body Text, Space After: 0 pt Chemically driven oil and gas production 2.6 Formatted: No bullets or numbering, Don't 2.6.1 PFOS and alternative chemistry adjust space between Latin and Asian text It is reported that PFOS is used in some parts of the world as surfactants in oil well stimulation Formatted: Font: 14 pt to recover oil trapped in small pores between rock particles. Oil well stimulation is in general a Formatted: Normal, No bullets or numbering variety of operations performed on a well to improve its productivity. The main two types of Formatted: Font: (Default) Lucida Sans operations are acidization matrix and hydraulic fracturing. Unicode Alternatives to PFOS are PFBS, telomer-based fluorosurfactants or polymers, perfluoroalkyl- Formatted: Font: Calibri, 11 pt substituted amines, acids, amino acids, and thioether acids. In most parts of the world where oil exploration and production are taking place, oil service companies engaged in provision of well stimulation services predominantly use formulation of alcohols, alkyl phenols, ethers, aromatic hydrocarbons, inorganic salts, methylated alcohols, alipathic fluorocarbons for oil well stimulation. Oil well stimulation services also involve corrosion control, water blocks/blockage

control, iron control, clay control, paraffin wax and asphaltene removal and prevention of fluid loss and diverting. Enhanced oil recovery operations have imbibed global best practices.

PFOS can be used as a surfactant in etching processes in the manufacture of compound semiconductors and ceramic filters. PFOS is then added as part of an etching agent, and rinsed out during the subsequent washing treatment. Desmear processes smooth the surface of a through-hole in printed circuit boards. PFOS can be used as a surfactant in the desmear agent, i.e. etching agent. PFOS is added into a desmear agent, and rinsed out during the washing treatment.Non-critical uses of PFOS are as edge bead removers, de-gluing agents and developing agents.

• PFOS is used as a component of a photoresist substance (see figure 2-4), including a Formatted: No bullets or numbering photo acid generator or surfactant; or of an anti-reflective coating, used in a photomicrolithography process to produce semiconductors or similar components of electronic or other miniaturized devices (see figure 2-5). Photoresist is a polymer material necessary to shape a circuit in the photolithographic process. PFOS is added to the photoresist agent to make photoresist soluble in water and to give surface activity. Since the photoresist agent is rinsed out during the photolithographic process, PFOS does not remain in semiconductors. • The manufacture of semiconductors includes a series of photolithography processes. Since diffused reflection would possibly disorder the shape of a circuit in design, anti-reflective coating is necessary to avoid disturbance during photolithographic processes. PFOS is used in anti-reflective coating agents to give surface activity and regulate reflective characteristics of the coating between the metal and resist layers (see figure 2-5). Since anti-reflective coating agents are rinsed out during the photolithographic process, PFOS does not remain in semiconductors. A number of resist suppliers sell top anti-reflective coating (TARC) and bottom anti-reflective coating (BARC), which are used in combination with deep ultra violet (DUV) photoresist. The process involves placing a thin, top coating on the resist to reduce reflective light, in much the same way and for the same purposes that eyeglasses and camera lenses are coated. Semiconductor manufacturing comprises up to 500 steps (see figure 2-3), involving four fundamental physical processes: • Implant • Deposition • Etch • Photolithography Photolithography is the most important of the four processes. It is essential for the successful implementation of the other three processes and, indeed, the overall production process. It shapes and isolates the junctions and transistors; it defines the metallic interconnects; it delineates the electrical paths that form the transistors; and it joins them together. Photolithography reportedly represents 150 of the total 500 steps. Photolithography is also integral to the miniaturization of semiconductors (RPA association, 2004). PFOS reduces the surface tension and reflection of etching solutions, properties that are important for precise photolithography in the semiconductor industry (photoresists and photo

masks). Small amounts of PFOS-based compounds are required during the following critical photolithography applications, which are crucial for achieving the accuracy and precision required to manufacture miniaturized high-performance semiconductor chips: • Ultra-fine patterning/photoresists as photo-acid generators and/or surfactants • Anti-reflective coatings as uniquely performing surfactants

Formatted: Font: (Default) Lucida Sans Unicode Formatted: List Paragraph1, Justified, Space 2.7 Electronics industry After: 6 pt 2.7.1 PFOS and alternative chemistry Formatted: No bullets or numbering, Don't Electrical and electronic equipment often requires hundreds of components and thousands of adjust space between Latin and Asian text processes. PFOS has many different uses in the electronics industry and is involved in many of the production processes needed for electric and electronic parts (see figure 2-2). PFOS-based chemicals are used in the manufacturing of digital cameras, cell phones, printers, scanners, satellite communication systems, radar systems and the like. The PFOS-related compounds are process chemicals, and the final articles are mostly PFOS-free. PFOS can be used as a surfactant in etching processes in the manufacture of compound semiconductors and ceramic filters. PFOS is then added as part of an etching agent, and rinsed out during the subsequent washing treatment. Desmear processes smooth the surface of a through-hole in printed circuit boards. PFOS can be used as a surfactant in the desmear agent, i.e. etching agent. PFOS is added into a desmear agent, and rinsed out during the washing treatment. The other processes involved are described in the discussions on the semiconductor industry (section 2.7.2) and metal plating (section 2.5).

Formatted: Font: 12 pt PFOS use in Electronics Industry (in Japan)

PFOS surface treatment fix-unit anti-reflective dispersion coating adhesive surface treatment photoresist solder paint desmear metal other use etching plating

semiconductor parts, modules photo masks PWB HDD Effect for other industries

Figure 2-2: PFOS use in electronics industry supply chain (Japan Electronics and Information Technology Industries Association Semiconductor Board)

2.7.2 Semiconductor industry Formatted: No bullets or numbering, Don't adjust space between Latin and Asian text PFOS and PFOS-based substances are chemicals required by the semiconductor industry for formulation of resists and anti-reflective coatings in high-end lithography. The manufacture of advanced semiconductor devices is not currently possible without the use of PFOS in "critical applications" such as photo resistant and anti-reflective coatings. PFOS is a process chemical; it does not remain in the final article – the semiconductor device. Semiconductor manufacturing comprises up to 500 steps (see figure 2-3), involving four fundamental physical processes: • Implant • Deposition • Etch • Photolithography Photolithography is the most important of the four processes. It is essential Formatted: Font: Calibri, 11 pt for the successful implementation of the other three processes and, indeed, Formatted: List Bullet 2, Space After: 6 pt, the overall production process. It shapes and isolates the junctions and Bulleted + Level: 1 + Aligned at: 0.88" + Tab after: 1.13" + Indent at: 1.13", Tab stops: transistors; it defines the metallic interconnects; it delineates the electrical 0.45", List tab paths that form the transistors; and it joins them together. Photolithography reportedly represents 150 of the total 500 steps. Photolithography is also integral to the miniaturization of semiconductors (RPA association, 2004).

Wafer Formatted: Font: Calibri, 11 pt, Font color: Wax Red Slurry Wafer Repeat Surfactant 20-40 times Diffusion/CVD Mask Diffusion/CVD Cr Eｔchant Resist Resist Patterning ARC Surfactant Developer Glass plate Polyimideolyimide....etcetc Probe Card Plating chemicals Assembly for Probe Card Assembly

Lead Frame Test Mask Synthetic resin Eｔchant Product Products

Figure 2-3: Different steps in semiconductor manufacturing where PFOS is used as an intermediate (The process in red is related to PFOS related substances. Source: Japan Electronics and Information Technology Industries Association Semiconductor Board)

PFOS reduces the surface tension and reflection of etching solutions, properties that are important for precise photolithography in the semiconductor industry (photoresists and photo masks). Small amounts of PFOS-based compounds are required during the following critical photolithography applications, which are crucial for achieving the accuracy and precision required to manufacture miniaturized high-performance semiconductor chips: • Ultra-fine patterning/photoresists as photo-acid generators and/or surfactants

• Anti-reflective coatings as uniquely performing surfactants Formatted: Indent: Left: -0.25", Don't adjust space between Latin and Asian text, Don't adjust space between Asian text and numbers Formatted: Font color: Red, English (United Wave length of Laser light for exposure device is very short. Kingdom) Then light can not attain to the bottom of resist. PAG can resolve this problem Formatted: List Paragraph1, Justified, Space After: 6 pt, Bulleted + Level: 1 + Aligned at: exposure 0.75" + Indent at: 1", Don't adjust space 1. Low surface tension between Latin and Asian text, Don't adjust 2. Low reflection space between Asian text and numbers ＋ 3. High acid durability acid（Ｈ） Formatted: Font: Calibri, 11 pt, Font color: 4. Thermal stability Red 5. High UV durability

酸発生剤に光が当ると酸（ＨGeneration of acid＋）を放出する 6. Dispersible

exposure露光

発生した酸（Ｈ＋）はポリマーのアルカリ不溶性保護基と反応してアルカリ可容基に変化させる。このAcid reacts with resist 反応は酸触媒反応で連続して反応を繰り返す。 No substitution of PFOS

Figure 2-4: Description of photoresist critical use of PFOS and its related substances in photolithography processes (Japan Electronics and Information Technology Industries Association Semiconductor Board) Note: 1 to 6 describe the important functions of PFOS and its related substances when used as a component of a photoresist substance.

PFOS is used as a component of a photoresist substance (see figure 2-4), including a photo acid generator or surfactant; or of an anti-reflective coating, used in a photomicrolithography process to produce semiconductors or similar components of electronic or other miniaturized devices (see figure 2-5). Photoresist is a polymer material necessary to shape a circuit in the photolithographic process. PFOS is added to the photoresist agent to make photoresist soluble in water and to give surface activity. Since the photoresist agent is rinsed out during the photolithographic process, PFOS does not remain in semiconductors. The manufacture of semiconductors includes a series of photolithography processes. Since diffused reflection would possibly disorder the shape of a circuit in design, anti-reflective coating is necessary to avoid disturbance during photolithographic processes. PFOS is used in anti-reflective coating agents to give surface activity and regulate reflective characteristics of the coating between the metal and resist layers (see figure 2-5). Since anti-reflective coating agents are rinsed out during the photolithographic process, PFOS does not remain in semiconductors. A number of resist suppliers sell top anti-reflective coating (TARC) and bottom anti-reflective coating (BARC), which are used in combination with deep ultra violet (DUV) photoresist. The process involves placing a thin, top coating on the resist to reduce reflective light, in much the same way and for the same purposes that eyeglasses and camera lenses are coated.

Formatted: Font: Calibri, 11 pt, Font color: Red

1. Low surface tension 2. Low reflection 3. High acid durability 4. Thermal stability Anti-reflective coating 5. High UV durability １００nm 6. Dispersible

abnormal normal No substitution of PFOS

Figure 2-5 : Description of anti-reflective coating critical use of PFOS and its related substances in photolithography processes (Japan Electronics and Information Technology Industries Association Semiconductor Board) Note: 1 to 6 describe the important functions of PFOS and its related substances when used as a component of a photoresist substance. Despite significant R&D in recent years, currently there are no replacement substances, for some of the specific uses of PFOS, that provide the critical functionality and equal the performance required at these technology levels. In the photolithography industry, few alternatives are available that would allow for the comprehensive substitution of PFOS in critical applications. Thus the new photolithography technologies, which in detail are trade secrets, use less photoresist per wafer, and the new photoresist formulations contain much lower concentrations of PFOS. Non-critical uses of PFOS are as edge bead removers, de-gluing agents and developing agents. 2.7.3 Photographic industry Formatted: No bullets or numbering, Don't adjust space between Latin and Asian text PFOS-based chemicals are used for the following purposes in mixtures, in coatings applied to Formatted: Font: 14 pt photographic films, papers, and printing plates (RPA association, 2004): Formatted: Heading 3, Left, Don't adjust space between Latin and Asian text • Surfactants Formatted: Heading 3, Space After: 0 pt, No bullets or numbering, Don't adjust space between Latin and Asian text • Electrostatic charge control agents

• Friction control agents

• Dirt-repellent agents

• Adhesion control agents

The uses of PFOS in this industry include coatings for surface tension, static discharge, adhesion Formatted: Heading 3, Don't adjust space control for analogue and digital imaging films, papers, and printing plates; and as a surfactant in between Latin and Asian text mixtures used to process imaging films.

Chapter 3: BAT/BEP Principles for Chemicals Management of Formatted: Font: (Default) Lucida Sans PFOS and PFOS-related SubstancesBest Environmental Practices Unicode, 14 pt, Bold, Font color: Text 2 (BEP) for Chemicals Management

Formatted: No Spacing1, Justified, Indent: General Guidance on Best Environmental Practices First line: 0.25", Space After: 6 pt (BEP)BAT/BEP Measures Water Management, Off-Gas and Solid Waste Management Handling and Knowledge of the Waste Flow Occupational Health and Safety Measures Formatted: Font: (Default) Lucida Sans Manufacturing BAT/BEP Measures Unicode, 14 pt, Bold, Font color: Text 2, English (United States) General BEP Measures applicable to handling all chemicals Formatted: Indent: Left: 0.25" BEP Measures for manufacturing of PFOS containing PFOS- related substances containing products Specific BEP measures when using PFOS and PFOS-Related Substances Formatted: Font: (Default) Lucida Sans BEP Measures for manufacturing of Alternatives to PFOS and Unicode, 14 pt, Bold, Font color: Text 2 PFOS-related Substances Formatted: Font: (Default) Lucida Sans Unicode, 14 pt, Bold, Font color: Text 2 BAT/Specific BEP Measures when using Alternatives to PFOS Formatted: Font: (Default) Lucida Sans Unicode, 14 pt, Bold, Font color: Text 2 and PFOS-related Substances Formatted: Font: (Default) Lucida Sans Unicode, 14 pt, Bold, Font color: Text 2 Formatted: Font: (Default) Lucida Sans Chapter 4: Unicode, 14 pt, Bold, Font color: Text 2 Formatted: List Paragraph, Numbered + Specific BEPBAT/BEP Measures for Acceptable Purposes Level: 1 + Numbering Style: A, B, C, … + Start at: 1 + Alignment: Left + Aligned at: 0.5" + Processes Indent at: 0.75" Formatted: Font: (Default) Lucida Sans A. BEPBAT/BEP for Photo-Imaging Unicode, 14 pt, Bold, Font color: Text 2 Formatted: Font: (Default) Lucida Sans B. BEPBAT/BEP for Photoresist and anti-reflective coatings Unicode, 14 pt, Bold, Font color: Text 2 for semiconductors Formatted: Font: (Default) Lucida Sans Unicode, 14 pt, Bold, Font color: Text 2 C. BEPBAT/BEP for etching agent for compound Formatted: Font: (Default) Lucida Sans Unicode, 14 pt, Bold, Font color: Text 2 semiconductors and ceramic filters Formatted: Font: (Default) Lucida Sans Unicode, 14 pt, Bold, Font color: Text 2 56

Formatted: Font: (Default) Lucida Sans D. BEPBAT/BEP for Aviation hydraulic fluids Unicode, 14 pt, Bold, Font color: Text 2 Formatted: Font: (Default) Lucida Sans E. BEPBAT/BEP for metal plating (hard metal plating) only Unicode, 14 pt, Bold, Font color: Text 2 Formatted: Font: (Default) Lucida Sans in closed-loop systems Unicode, 14 pt, Bold, Font color: Text 2 F. BEPBAT/BEP for certain medical devices (such as Formatted: Font: (Default) Lucida Sans Unicode, 14 pt, Bold, Font color: Text 2 ethylene tetraethylene copolymer (ETFE) layers and Formatted: Font: (Default) Lucida Sans Unicode, 14 pt, Bold, Font color: Text 2 radio opaque ETFE production, in vitro-diagnostic Formatted: Font: (Default) Lucida Sans medical devices, and CCD colour filters) Unicode, 14 pt, Bold, Font color: Text 2 Formatted: Font: (Default) Lucida Sans G. BEPBAT/BEP for Fire Fighting Foam Unicode, 14 pt, Bold, Font color: Text 2 Formatted: Font: (Default) Lucida Sans H. BEPBAT/BEP for insect baits for control of leaf-cutting Unicode, 14 pt, Bold, Font color: Text 2 Formatted: Font: (Default) Lucida Sans ants from Atta spp. and Acromyrmex spp. Unicode, 14 pt, Bold, Font color: Text 2

Formatted ... Specific BEPBAT/BEP Measures for Specific Exemptions Formatted: Indent: Left: 0.25" Formatted ... A. BEPBAT/BEP for photo masks in the semiconductor and Formatted ... liquid crystal display (LCD) industries Formatted ... Formatted ... B. BEPBAT/BEP for metal plating (hard metal plating) Formatted ... C. BEPBAT/BEP for metal plating (decorative plating) Formatted ... D. BEPBAT/BEP for electric and electronic parts for some Formatted ... Formatted ... colour printers and colour copy machines Formatted ... E. BEPBAT/BEP for insecticides for control of red imported Formatted ... Formatted ... fire ants and termites Formatted ... F. BEPBAT/BEP for chemically driven oil production Formatted ... Formatted G. BEPBAT/BEP for carpets ... Formatted ... H. BEPBAT/BEP for leather and apparel Formatted ... I. BEPBAT/BEP for textiles and upholstery Formatted ... Formatted ... J. BEPBAT/BEP for paper and packaging Formatted ... K. BEPBAT/BEP for coatings and coating additives Formatted ... Formatted L. BEPBAT/BEP for rubber and plastics ... Formatted ... Formatted ... Chapter 5: Best Environmental Practices (BEP) for Chemicals Formatted ... Formatted ... Management Formatted: Font color: Text 2 57

Formatted: Font: +Body, English (United Kingdom) Chapter 3: Comment [A81]: This and the following chapter have been reformated to allow for a Best Environmental Practices (BEP) for Chemicals Management better flow of infomation and to adhere to a similar structure as used in Chapter 2. The content of these chapters has been consolidated from the original text and has been General Guidance on Best Environmental Practices (BEP) expanded in places Formatted: Font: (Default) Lucida Sans The following subchapters contain specific areas in relation to the environmental management Unicode systems (EMS) that could improve environmental performance of an installation including the Formatted: Font: (Default) Lucida Sans increased awareness of the workers/employees handling chemicals. Unicode BEP describes the application of the most appropriate combination of environmental control Formatted: Font: (Default) Lucida Sans Unicode, 14 pt, Bold, Font color: Text 2 measures and strategies, which includes a behaviour that relates to the continuous improvement of environmental performance. BEP provides the framework for ensuring the Formatted: Font color: Text 2 identification, adoption and adherence to management options that remain important and can Formatted: Font: (Default) Lucida Sans Unicode, 12 pt, Bold, Font color: Text 2 play a role in improving environmental performance of the installation. In general, good housekeeping/management techniques/tools often prevent emissions. Formatted: Indent: Left: 0.5" The main ecological advantages achieved through the use of BEP management methods include: Formatted: List Paragraph, Bulleted + Level: 2 + Aligned at: 0.75" + Indent at: 1" savings in consumption of: chemicals/auxiliaries Formatted: Indent: Left: 0.25" fresh water Formatted: List Paragraph, Bulleted + Level: 2 + Aligned at: 0.75" + Indent at: 1" energy minimizing the amount of: Formatted: Font: (Default) Calibri, 11 pt solid waste Formatted: Font: (Default) Calibri, 11 pt ecological loads in wastewater Formatted: Font: (Default) Calibri, 11 pt off-gas emissions (might not relate to all processes) Formatted: Normal, Justified Another advantage is an improved workplace situation. Well-trained employees are a Comment [A82]: Please include this prerequisite for implementing BEP system measures. Limiting factors for improving existing reference equipment also need to be taken into consideration with the application of BEP, e.g. new Formatted: Font: (Default) Calibri, 11 pt equipment has to be rebuilt/modified or installed (automated dosing systems, etc.). These Comment [A83]: http://www.ifc.org/wps/wcm/ applicability factors can be limited due to the fact that the measures may be too cost-intensive connect/Topics_Ext_Content/IFC_External_Corporat e_Site/IFC+Sustainability/Sustainability+Framework or due to technological/logistics or a space problem (Schönberger et al., 2005). For references /Environmental,+Health,+and+Safety+Guidelines/ on general examples of Good International Industry Practice (GIIP), including environmental, health, and safety guidelines, please see International Finance Corporation’s website [ ] that also Comment [A84]: “Draft revised general contains a list of specific industry sector guidelines. technical guidelines for the environmentally sound General technical guidelines for the environmentally sound management of wastes have been management of wastes consisting of, containing or contaminated with persistent organic pollutants” at developed under the Basel Convention. For a general technical guideline, please see [ ] and for http://www.basel.int/Implementation/TechnicalMa a detailed guidance on the environmentally sound management of PFOS-containing waste tters/DevelopmentofTechnicalGuidelines/POPs/tabi d/2381/Default.aspx please see [ ]. Please ensure to link to the most recent revised Environmental Management Systems (EMS) document. Comment [A85]: “Draft revised technical A number of environmental management techniques are determined as BEP. The scope and guidelines for the environmentally sound ... nature of an EMS will generally be related to the nature, scale and complexity of the installation, Formatted: Font: 11 pt, Font color: Blue and the range of environmental impacts it may have. For example, ISO 14001 sets out criteria Formatted: Indent: Left: 0.5" for an EMS [ ]. Formatted: Font: 12 pt, Bold, Font color: Blue Comment [A86]: http://www.iso.org/iso/home/ standards/management- ... 59

BEP is to implement and adhere to an EMS that incorporates the following features, as appropriate, for individual circumstances: Definition of an environmental policy for installation by top management (its commitment is regarded as a precondition for a successful application of other features of the EMS). Planning and establishing of the necessary procedures. Implementation of the procedures, paying particular attention to: Structure and responsibility Training, awareness and competence Communication Employee involvement Documentation Efficient process control Maintenance programme Emergency preparedness and response Safeguarding compliance with environmental legislation Checking of performance and taking of corrective action, paying particular attention to: Monitoring and measurement Corrective and preventive action Maintenance of records Perform independent (where feasible) internal auditing to determine whether or not the EMS conforms to planned arrangements and has been properly implemented and maintained Formatted: Font: +Body

Formatted: Font: +Body, 11 pt Additional Considerations Formatted: Font: 11 pt, Font color: Blue Three additional features are considered as supporting measures; their absence, however, is Formatted: Indent: Left: 0.5" generally not inconsistent with BEP: Formatted: Font: 12 pt, Bold, Font color: Blue Examination and validation of the management system and audit procedure by an accredited certification body or an external EMS verifier Preparation and publication (and possibly external validation) of a regular environmental statement describing all the significant environmental aspects of the installation, allowing for year-by-year comparison against environmental objectives and targets as well as with sector benchmarks as appropriate Implementation and adherence to an internationally accepted EMS This last voluntary step could give higher credibility to the EMS, particularly internationally accepted and transparent standards, such as ISO9001 and ISO14001. Non-standardized systems can in principle be equally effective provided that they are properly designed and implemented. Formatted: Indent: Left: 0.5" Specific Education and Training of Employees Formatted: Font: 12 pt, Font color: Blue The following training and education opportunities could be beneficial for raising awareness at Formatted: Font: 12 pt, Bold, Font color: Blue work for sound chemical management in general: Process- and machinery-specific training to increase the level of environmental awareness Appropriate education of workers concerning handling of chemicals and auxiliaries, especially in case of hazardous substances

Maintenance of technical equipment (machines in production as well as abatement and recovery devices); machinery checking (e.g. pumps, valves, level switches); general maintenance by specialized companies at regular intervals; and checking of the burner air inlet at regular intervals Leak control of chemicals when stored and during processing Filter maintenance (periodically cleaning and controlling) Calibration of equipment for chemicals measuring and dispensing devices

Industrial Considerations Formatted: Font: 11 pt, Font color: Blue It is also important for industry to consider the following potential features of the EMS: Formatted: Indent: Left: 0.5" At the plant design stage, give consideration to the environmental impact of the Formatted: Font: 12 pt, Bold, Font color: Blue eventual decommissioning of the unit Give consideration to the development of cleaner technologies Where practicable, conduct sector benchmarking on a regular basis, including energy efficiency and energy conservation activities, choice of input materials, emissions to air, discharges to water, consumption of water and generation of waste Ensure the provision of full details of the activities carried out on-site: Descriptions of the waste treatment methods and procedures in the place of installation Diagrams of the main plant items that have some environmental relevance, together with process flow diagrams (schematics) Details on the control system philosophy and how the control system incorporates the environmental monitoring information Details on how protection is provided during abnormal operating conditions such as momentary stoppages, start-ups, and shutdowns Instruction manual Operational diary Annual survey of the activities carried out and the waste treated, which contains a quarterly balance sheet of the waste and residue streams, including the auxiliary materials used for each site Have good housekeeping procedures in place, which will also cover the maintenance procedure, and an adequate training programme, covering the preventive actions that workers need to take on health and safety issues and environmental risks Have a close relationship with the waste producer/holder so that the customers' sites implement measures to produce the required quality of waste necessary for the waste Formatted: Font: 14 pt, Bold treatment process to be carried out Formatted: Font: (Default) Lucida Sans Have sufficient staff available on duty with the requisite qualifications at all times. All Unicode, 12 pt, Bold, Font color: Text 2 personnel should undergo specific job training and further education Formatted: Font: (Default) Lucida Sans Unicode, Bold, Font color: Text 2

Formatted: Normal, Justified, Space After: 6 pt General BEP Measures applicable to handling all chemicals Formatted: Font: Calibri, 11 pt This section describes principles, measures and safety precautions that apply to all types of Formatted: Font: (Default) Calibri, 11 pt, (Asian) Chinese (Simplified, PRC), (Other) chemicals and industries handling them. Guidelines that apply to specific process categories are German (Germany) described in the following chapters. Formatted: Font: 12 pt, Font color: Blue Formatted: Indent: Left: 0.5" Chemical Knowledge, Storage, Handling, Dosing, Dispensing and Transport Formatted: Font: +Body, Bold, Font color: Blue 61

In storing, handling, dosing, dispensing, and transporting of any chemical, caution should be used. Before ordering/receiving any chemical review the Safety Data Sheet (SDS). If possible, avoid CMR (Carcinogenic, Mutagenic, Reproductive Toxin) and PBT (Persistent, Bioaccumulative and Toxic) substances, and substances that can degrade to CMR or PBT substances (see SDS Section 2, 11, and 12) In case a complete SDS is not available from one supplier, order the product from an alternative supplier that provides a complete SDS Gather information from your supplier on amounts of residual raw materials, by- products and potential degradation products in the product you intend to order Reject leaking or dented containers upon receiving Proper storage according to the instruction of the most up to date material safety data sheet (SDS), preferably in Global Harmonization Standard (GHS) format Before handling any chemical, review the SDS carefully Proper labelling of containers and equipment; storage in special compartments, containers or locations for toxic and explosive chemicals to avoid leakage and spill Dosing and dispensing without spilling in automated dosing systems

Minimization/Optimization of the Chemicals Used Formatted: Font: 12 pt, Bold, Font color: Blue Minimize the use of all chemicals and auxiliary materials Formatted: Font: +Body, Bold, Font color: Measure, mix and dose chemicals carefully to avoid losses Blue Minimize residual, left-over chemicals, by calculating exactly how much is needed for Formatted: Indent: Left: 0.25", First line: the process step 0.25" Substitution of overflow rinsing or minimization of water consumption in overflow Formatted: List Paragraph, Bulleted + Level: 1 + Aligned at: 0.25" + Indent at: 0.5" rinsing by means of optimized process control Formatted: Font: 12 pt Reuse of rinsing baths, including final rinsing baths Reversing of current flows in continuous washing Formatted: Font: 12 pt Cleaning and recycling of process water – where possible Formatted: Font: 12 pt Use of low emission preparation agents through the total supply chain where possible Use of low emission options

Equipment Formatted: Indent: Left: 0.25", First line: Use equipment, pipes, valves, etc. that are suited to handle the material (e.g., corrosion 0.25" resistance) top ensure a long equipment life and to avoid equipment breakdown and Formatted: List Paragraph, Bulleted + Level: 1 + Aligned at: 0.25" + Indent at: 0.5" leaks To prevent releases to the environment via air, install dust collectors, scrubbers or similar devices Formatted: Font: 11 pt Collect all waste and leftover chemicals from all processes and dispose of them in accordance to guidance provided in the product SDS and in compliance with local rules Formatted: Font: 12 pt and regulations. In general, the drain is not an appropriate outlet for waste. Formatted: Indent: Left: 0.25", First line: 0.25"

Formatted: List Paragraph, Bulleted + Level: 1 Leak and Spill Procedure + Aligned at: 0.25" + Indent at: 0.5" Follow instructions according to information provided on the SDS Formatted: Font: 11 pt Make such a procedure part of the operator training to enhance preparedness Formatted: Font: 12 pt, Font color: Blue

Formatted: Indent: Left: 0.25", First line: Emissions Reductions and Waste Management 0.25" Formatted: Font: Bold, Font color: Blue 62

The following measures could be considered for water management, off-gas and solid waste management: Follow all procedures as outlined above Adhere to waste disposal methods given in the SDS For guidance on sound management of waste, please follow guidance provided by the Basel Convention [see above].

3. BAT/BEP principles for chemicals management of PFOS and PFOS-related Substances

3.1 General BAT/BEP measures This section describes principles, measures and safety precautions that apply to all types of products and industries related to PFOS and PFOS-releated substances in the following areas: • Storage, handling, dosing, dispensing and transport • Improved knowledge of the raw materials used • Minimization/optimization of the chemicals used • Equipment

Guidelines that apply only to specific process categories are described in chapter 4.

3.1.1 Storage, handling, dosing, dispensing and transport of PFOS and PFOS-related Substances When storing and handling PFOS and PFOS-related substances, indicate that such substance(s) is being stored in thea defined location. In storing, handling, dosing, dispensing, and transporting PFOS containing-products, caution should be used to ensure: • Proper storage according to the instruction of the material safety data sheet (MSDS). • Proper labelling of containers and equipment in special compartments, containers or locations for toxic and explosive chemicals to avoid leakage and spill. • Dosing and dispensing without spilling in automated dosing systems. • Use of only as much PFOS or PFOS-related substances as essentially needed for the process, by measuring and recording the PFOS or PFOS-related substances consumption.

3.1.2 Improved knowledge of the raw materials used

When handling products and preparations containing PFOS or PFOS-related substances, the following relevant information cshould be collected and analyzed to plan proper handling: • Auxiliaries and basic chemicals information from the supplier concerning proper storage and handling; and environmental characteristics (COD, BOD5, aquatic toxicity, degree of biodegradation/bioelimination, content of nitrogen, phosphorous, sulphur, adsorbable organic halogens (AOX)-relevant compounds, kind and amount of volatile compounds, emission factor, health and safety aspects).

• Information from the supplier concerning types of preparation agents, amounts of residual monomer, impurity (by-product) content, and solvent contents of the raw materials. • Chemical and physical characteristics to be considered for proper handling.

3.1.3 Minimization/optimization of the chemicals used

Minimization and optimization of PFOS (or PFOS-related)-containing chemicals may be achieved by taking the following into consideration: • Avoiding any kind of applied fluorochemicalsfluorinated substances and auxiliaries that may have a potential to transform into and/or emit PFOS or PFOS-related substances. • Using fluorinated substances fluorochemicals that do not transform and emit PFOS or PFOS-related substances, and performing regular revising of the recipes that include auxiliaries and chemicals with a high degree of biodegradation/bioelimination. Low human and ecological toxicity, low volatility and low smellodour intensity are preferred. • Avoiding surpluses of applied chemicals and auxiliaries. • Avoiding, if possible, add-on devices (spraying, foam application, special padding devices).Consider application equipment that uses the least amount of chemical products needed • Decreasing the use of PFOS or PFOS-related substances to the lowest possible level if unable to replace them.

3.1.4 Equipment

When choosing and using equipment, the following could be considered: • Using equipment made of materials that sustain corrosion. • Limiting the use of the equipment to PFOS or its salts only. • Installing ventilation where scattering is expected and, to prevent releases into the environment, installing a dust collector, scrubber or similar devices. • Using material that is not likely to corrode for piping from equipment as well as for wastewater.

• Separate collection of solid waste that has an unknown quantity of PFOS and related substances. • Storing of this waste in a controlled landfill (i.e. a landfill with no leakage to the surrounding environment). • Where possible, Rreuse and recyclingrecycle of known “PFC-free” product wastes (RPA association with BRE ENV., 2004). • Irreversible destruction of waste with an unknown quantity of PFOS and related substances at a minimum of 1100 °C. • Avoidance of mixing PFOS-free solutions or wash water with solutions containing PFOS.

3.2.1 Removal of PFOS and PFOS-related substances from Waste Water Bby Formatted: Font: 12 pt, English (United Kingdom) Adsorption Formatted: Font: 12 pt, Font color: Blue Formatted: Normal By selecting suitable activated carbon and optimized flow rates, up to 99% of PFOS can be Formatted: Font: 12 pt, Italic, Font color: Blue removed from wastewater by adsorption onto activated carbon (Fath, 2008). Comment [A87]: Please include this When using special basic ion exchange resins, a reduction of more than 99% of the initial reference PFOS concentration can be achieved (Zentralverband Oberflächentechnik, 2011). Either Comment [A88]: Please include this weak base or strong base anion exchangers are able to reduce the PFOS concentration to reference <10µg/l (Neumann, 2011). Comment [A89]: Please include this reference The recommendations of the Stockholm Convention’s COP-5 must be taken into account Comment [A90]: Please provide a link to the when using any adsorption method that requires a final destruction of the adsorbent that recommendation contains PFOS or PFOS-related substances at the end-of-life so as not to deposit such wastes improperly. The destruction could be done in a BAT hazardous waste incineration plant at temperatures of at least 1100°C and with a residence time of 2 seconds. Please consult Basel Convention Guidance [ ] for further details. Comment [A91]: “Draft revised technical guidelines for the environmentally sound management of wastes consisting of, containing or contaminated with perfluorooctane sulfonic acid, its salts and perfluorooctanesulfonyl fluoride” at Further, technical guidelines for the environmentally sound management of wastes http://www.basel.int/Implementation/TechnicalMa consisting of, containing or contaminated with PFOS have been developed under the Basel tters/DevelopmentofTechnicalGuidelines/POPs/tabi d/2381/Default.aspx Convention and provide detailed guidance on the environmentally sound management of PFOS-containing waste. Formatted: Indent: Left: 0"

3.3 Handling and knowledge of the waste flow The following know-how needs to be taken into account for the management of waste flows: i) the treatments to be carried out, ii) the types and origins of waste to be accepted and treated, and iii) the handling procedures under consideration and their associated risks. The monitoring of waste flow involves implementation of the following procedures: • Pre-acceptance procedure • Acceptance procedure • Different sampling procedures • Reception facility

BAT and BEP for each of these areas are discussed in the next four sections. In addition, for updated information, please consider consulting adequate reference documents published under the Basel Convention. 3.3.1 Pre-acceptance procedure

Implementing the pre-acceptance procedure could consider at least the following items: • Tests for the incoming waste with respect to the planned treatment. • All necessary information received on the nature of the processes producing the waste, including the variability of the process. Personnel dealing with the pre-acceptance procedure need to be able to deal with all questions relevant to waste treatment in the waste treatment facility. • A system for providing and analyzing representative samples of the waste from the production process producing such waste from the current holder. • A system for carefully verifying, if not dealing directly with the waste producer, the information received at the pre-acceptance stage, including the contact details of the waste producers and an appropriate description of waste composition and its hazardousness. • An existing national waste code, provided or developed. • Appropriate treatment for each waste to be received at the installation by identifying a suitable treatment method for each new waste enquiry and a clear methodology in place to assess the treatment of waste, which considers the physico-chemical properties of the individual waste and the specifications for the treated waste. • Waste characterization laboratory testing necessary to establish the concentration of PFOS and PFOS-related substances, if required. 3.3.2 Acceptance procedure

The acceptance procedure involves implementing a clear and specified system that allows the operator to accept wastes at the receiving plant only if a defined treatment method and disposal/recovery route for the output of the treatment are determined. Planning for this procedure involves guaranteeing that the necessary storage treatment capacity and dispatch conditions (e.g. acceptance criteria of the output by the other installation) are also respected: • Measures in place to fully document and deal with acceptable wastes arriving at the site, such as a pre-booking system, e.g. to ensure that sufficient capacity is available. • Clear and unambiguous criteria for the rejection of wastes and the reporting of all non- conformances. • A system for identifying the maximum capacity limit of waste that can be stored at the facility. • Visual inspection of the waste IN to check compliance with the description received during the pre-acceptance procedure. For some liquid and hazardous waste, this may not be applicable.

3.3.3 Sampling procedures

Implementation of different sampling procedures for different incoming waste vessels delivered in bulk and/or containers could contain the following items:

• Sampling procedures based on a risk approach, which could consider the type of waste (e.g. hazardous or non-hazardous) and the knowledge of the customer (e.g. waste producer). • Relevant physico-chemical parameters of all registered waste materials. • Different sampling procedures for bulk (liquid and solids), large and small containers, and laboratory samplers. The number of samples to be taken should increase with the number of containers. In extreme situations, all small containers must be checked against the accompanying paperwork. The procedure should contain a system for recording the number of samples and degree of consolidation. • Details of the sampling of wastes in drums within designated storage, e.g. the time scale after receipt. • Samples prior to acceptance. • Maintenance of a record at the installation of the sampling regime for each load, together with a record of the justification for the selection of each option. Includes a system for determining and recording. • A suitable location for the sampling points. • The capacity of the vessel sampled (for samples from drums, an additional parameter would be the total number of drums). • The number of samples and degree of consolidation. • Operating conditions at the time of sampling. • A system to ensure that the waste samples are analyzed. • A temporary storage, in case of cold ambient temperatures, to allow sampling after defrosting. This may affect the applicability of some of the above items. Formatted: No bullets or numbering 3.3.4 Reception facility

The reception facility could cover at least the following issues: • A laboratory to analyze all the samples at the speed required by BAT. Typically this requires a robust quality assurance system, quality control methods and the maintenance of suitable records for storing the analysis results. Particularly for hazardous wastes, this often means that the laboratory needs to be on site. • A dedicated quarantine waste storage area as well as written procedures to manage non-accepted waste. Wastes can be temporarily stored there safely if the inspection or analysis indicates that they fail to meet the acceptance criteria (including, e.g. damaged, corroded or unlabelled drums). Such storage and procedures could be designed and managed to promote rapid management (typically a matter of days or less) to find a solution for that waste. • A clear procedure to deal with wastes when inspection and/or analysis prove that they do not fulfil the acceptance criteria of the plant or do not fit with the waste description received during the pre-acceptance procedure. The procedure includes all measures, as required by the permit or national/international legislation, to: inform competent authorities and safely store the delivery for any transition period or reject the waste and send it back to the waste producer or to any other authorized destination. • Waste in the storage area only after acceptance of the waste. • Clearly marked inspection, unloading and sampling areas on a site plan. • Sealed drainage system.

• Qualification and regular training of the personnel involved in the sampling, checking and analysis procedures. • Application of a waste tracking system unique identifier (label/code) to each container at this stage. The identifier will contain at least the date of arrival on site and the waste code.

3.4 Occupational health and safety measures This section describes procedures, equipment and measures related to PFOS and PFOS-related substances handling, special and personal protection when working with PFOS and PFOS-related substances and first aid procedures. Before storing handling, dosing , dispensing , and transporting PFOS or any PFOS-containing chemical, make sure to review the latest available up to date version of its Safety Data Sheet (SDS). In case a complete SDS is not available from onethe supplier, do not use that product and order the product from an alternative supplier that provides a complete SDS. 3.4.1 PFOS and PFOS-related Chemicals Handling precautions

For most recent information, please consult an up-to-date product SDS in GHS format.

Leak and spill detection procedures: • Shut off source of spill if possible to do so without hazard. • Contain the spill by diking. • Absorb spillage with clay, sawdust, or other absorbent material. • Place all spilled material, contaminated dirt, and other contaminated materials in approved drums for disposal.

Waste disposal: • Always dispose of according to local/national regulations.

Handling and special equipment: • Do not get PFOS (or PFOS-related chemical)-containing products in eyes, on skin or clothing. • Do not take it internally.ingest • Do not breathe vapours. • Keep away from heat, sparks, and open flames.Refill

Refill: Formatted: Normal, Justified, Space After: 0 When refilling the PFOS- or PFOS-related product containing agent: pt • Wear proper personal protective equipment Formatted: Font: Calibri, 11 pt, Not Bold • Handle the product indoors • Minimize number refills necessary • Avoid spills and overflows, use secondary containers to catch any spilled material • Prevent the product from remaining in equipment and take measures to recover it as much as possible Formatted: Indent: Left: 0" Storage requirements: • Store in a cool dry place away from heat, sparks, and open flames.

• Store in a well-ventilated area.

3.4.2 Special and personal protection: PFOS and PFOS-related Chemicals

For most recent information, please consult an up-to-date product SDS in GHS format. Formatted: Font: Calibri, 11 pt Formatted: Normal, No bullets or numbering • Mechanical ventilation: the use of mechanical ventilation is recommended whenever the PFOS (or PFOS-related)-containing product is used in a confined space. Otherwise, assure use in an area where there is natural air movement. • Respiratory protection: in operations where the vapour can be released, wear a respirator with organic vapour canister or cartridge. • Protective gloves: rubber or neoprene. • Eye protection: goggles. • Additional protective equipment: eyewash bottles or other rinsing equipment should be accessible.

3.4.3 First aid procedures

Formatted: Heading 3, Left

For most recent information, please consult an up-to-date product SDS in GHS format.

For eyes: • Immediately flush with plenty of water for at least 15 minutes. • Contact a physician if irritation persists. For skin: • Flush skin with water or wash with mild soap and water if available. • Remove contaminated clothing. • Contact a physician if irritation persists.

For inhalation: • Remove to fresh air. • If breathing has stopped, give artificial respiration. • Keep body warm and quiet and get medical attention.

For ingestion: • If conscious, immediately induce vomiting by giving two glasses of water and sticking finger down the throat. • Get immediate medical attention. • After patient has vomited, give milk, water or sodium bicarbonate in water to drink. Never give anything by mouth to an unconscious or convulsing person.

3.5 Manufacturing BAT/BEP measures Formatted: Font: 11 pt 3.5.1 BAT/BEP Measures for Manufacturing of PFOS Containing or PFOS-Related Formatted: Font: (Default) Lucida Sans Substances Containing Products Unicode, 11 pt, Bold, Font color: Text 2 • In case such products still need to be manufactured, the manufacturer should employ Formatted: List Paragraph, Bulleted + Level: 1 technology to minimize worker exposure and to minimize emissions to the environment + Aligned at: 0.25" + Indent at: 0.5" which includes water, air and soil Formatted: Font: 12 pt • Information provided in the previous chapters and in Chapter 5 is applicable and should Formatted: Font: 11 pt be utilized • Technology should be deployed to minimize unreacted raw material and byproduct Formatted: Font: 12 pt content in the products sold Formatted: Font: 12 pt • Information on unreacted raw material and byproduct content in products sold should Formatted: Indent: Left: 0.25" be made public to all customers and interested parties Formatted: Font: 12 pt, Bold, Font color: Blue, English (United Kingdom) Removal of PFOS and PFOS-related substances from Waste Water Formatted: Normal, Indent: Left: 0.25", First By Adsorption line: 0.25" Formatted: Font: 12 pt, Italic, Font color: Blue By selecting suitable activated carbon and optimized flow rates, up to 99% of PFOS can be Formatted: Indent: Left: 0.5", Hanging: removed from wastewater by adsorption onto activated carbon (Fath, 2008). 0.15", Don't adjust space between Latin and Asian text When using special basic ion exchange resins, a reduction of more than 99% of the initial PFOS Formatted: Font: 12 pt, Bold concentration can be achieved (Zentralverband Oberflächentechnik, 2011). Either weak base or Formatted: Font: +Body, 11 pt, Bold, Not strong base anion exchangers are able to reduce the PFOS concentration to <10µg/l (Neumann, Italic 2011). Comment [A92]: Please include this reference The recommendations of the Stockholm Convention’s COP-5 must be taken into account when Comment [A93]: Please include this using any adsorption method that requires a final destruction of the adsorbent that contains reference PFOS or PFOS-related substances at the end-of-life so as not to deposit such wastes improperly. Comment [A94]: Please include this The destruction could be done in a BAT hazardous waste incineration plant at temperatures of reference at least 1100°C and with a residence time of 2 seconds. Please consult Basel Convention Comment [A95]: Please provide a link to the Guidance [ ] for further details. recommendation Comment [A96]: “Draft revised technical guidelines for the environmentally sound management of wastes consisting of, containing or contaminated with perfluorooctane sulfonic acid, its Specific BEP Measures when Using PFOS and PFOS-Related Substances salts and perfluorooctanesulfonyl fluoride” at When using PFOS or a PFOS-related substance, select a product that has a verified http://www.basel.int/Implementation/TechnicalMa tters/DevelopmentofTechnicalGuidelines/POPs/tabi lowest possible amount of unreacted raw materials, by-products and potential d/2381/Default.aspx degradation products present Apply all BEP principles from above and adhere to BEP principles for your particular Formatted: Font: (Default) Lucida Sans process outlined in Chapter 4 Unicode, 12 pt, Bold, Font color: Text 2 Follow instructions given on the most recent SDS, preferably the SDS should adhere to Formatted: Font: (Default) Lucida Sans Unicode, 12 pt, Bold, Font color: Text 2 GHS format and be provided in a local language version Have dedicated equipment in your facility that only runs processes with PFOS and/or Formatted: Font: (Default) Lucida Sans Unicode, Bold, Font color: Text 2 PFOS-related substances Formatted: Font: 11 pt When a business operator handling PFOS (excluding a transport operator to whom transport is entrusted) transports it, it is recommended that measures be taken to Formatted: Font: Bold, Italic Formatted: Space After: 6 pt 70

prevent a container that stores PFOS from overturning. The container must be able to withstand the physical impact in case of an accident Formatted: Font: 11 pt Formatted: No bullets or numbering Indication of storage location Formatted: Font: +Body, 12 pt, Bold When storing and handling PFOS and PFOS-related substances, indicate that such substance(s) is Formatted: Font: +Body, Bold being stored in the defined location. Formatted: Indent: Left: 0.25", No bullets or Refill numbering, Don't adjust space between Latin and Asian text When refilling the PFOS- or PFOS-related product containing agent: Formatted: No bullets or numbering, Don't Handle the product indoors adjust space between Latin and Asian text Minimize number refills necessary Formatted: Font: +Body, 12 pt, Bold Avoid spills and overflows, use secondary containers to catch any spilled material Formatted: Font: +Body, Bold Prevent the product from remaining in equipment and take measures to recover it as much Formatted: Justified, Space After: 6 pt, as possible Outline numbered + Level: 1 + Numbering Style: Bullet + Aligned at: 0" + Tab after: 0.25" + Indent at: 0.25" Formatted: Font: Calibri, 11 pt 3.5.2 BAT/BEP Measures for Manufacturing of Alternatives to PFOS and PFOS- Formatted: Font: 11 pt Formatted: Font: (Default) Lucida Sans Related Substances Unicode, 11 pt, Bold, Font color: Text 2 • The manufacturer should employ technology to minimize exposure to workers and minimize emissions to the environment which includes water, air and soil Formatted: Font: 12 pt • The content of all previous chapters on BEP apply and should be utilized • Technology should be deployed to minimize unreacted raw material and byproduct content in the products sold • Information on unreacted raw material and byproduct content in products sold should be made public to all customers and interested parties Formatted: Font: +Body Formatted: List Paragraph

Formatted: Font: (Default) Lucida Sans 3.6 Specific BAT/BEP measures when using Alternatives to PFOS and Unicode, 12 pt, Bold, Font color: Text 2 PFOS-related Substances Formatted: Font: (Default) Lucida Sans • Avoid any material that may contain PFOS and/or PFOS-related substances as by- Unicode, 12 pt, Bold, Font color: Text 2 products or that can potentially degrade to form them Formatted: Font: (Default) Lucida Sans Unicode, Bold, Font color: Text 2 • Avoid any material that may contain long-chain fluorinated materials [for a definition, Formatted: Font: 12 pt please see the following OECD website: ], including as by-products or that can potentially degrade to form them Comment [A97]: http://www.oecd.org/ehs/pfc/ • Avoid – if possible – alternative products that contain an unknown amount or high levels of unreacted raw materials and by-products Formatted: Font: 12 pt • Apply all BEP principles from above and adhere to BEP principles for your particular process outlined in Chapter 4 and 5 • Follow instructions given on the most recent SDS, preferably the SDS should adhere to GHS format and be provided in a local language version Formatted: Indent: Left: 0.5", No bullets or numbering

Chapter 4: Formatted: Font: (Default) Lucida Sans Specific BAT/BEP Measures for Acceptable Purposes Processes Unicode, 14 pt, Bold, Font color: Text 2 It is important to be aware that good chemical management procedures are excellent tools to Formatted: Font: (Default) Lucida Sans utilize to limit chemicals from entering the environment. Moreover, adhering to these Unicode, 14 pt, Bold, Font color: Text 2 procedures becomes more important when the potential exists to release harmful chemicals to the environment and/or to release chemicals that could transform in the environment to become harmful to the environment and/or to release chemicals that will be persistent in the Formatted: Font: 12 pt, Bold, Font color: Text environment. The previous chapters focussed on general aspect applicable broadly. The 2 following chapters will address BAT/BEP measures specific to “Acceptable Purpose” and Formatted: Font: +Body, 12 pt, Bold, Font “Specific Exemption” applications (see Chapter 2) and apply whether PFOS and PFOS-related or color: Text 2 their alternatives are in use. Formatted: Left, Indent: Left: 0.5", Space After: 0 pt Formatted: List Paragraph, Left, Space After: BAT/BEP for Photo-Imaging 0 pt • The content of all previous general chapters on BEPBAT/BEP apply and should be utilized Formatted: Font: +Body, 11 pt Formatted: Normal, No bullets or numbering No further specific information on BEPBAT/BEP related topics on the photo-imaging Formatted: Font: +Body, 11 pt processes discussed in this report could be found. Formatted: Font: +Body, 11 pt

Formatted: Font: +Body, 11 pt

Formatted: Indent: Left: 0" BEPBAT/BEP for Photoresist and Anti-Reflective Coatings for Semiconductors Formatted: Font: 12 pt, Bold, Font color: Text • The content of all previous general chapters on BEPBAT/BEP apply and should be utilized 2 • For general environmental, health, and safety guidelines for semiconductors & other Formatted: Font: 12 pt, Bold, Font color: Text electronics manufacturing, see for example, [ ] 2 • Produce, distribute, store and consume the products in closed systems to prevent Formatted: Font: 12 pt, Bold, Font color: Text workplace exposure 2 • Use product only in explosion-proof equipment Formatted: Font: 12 pt, Bold, Font color: Text • Ground and bond all containers and handling equipment 2 • Adhere to a rigorous quality control strategy, special tools and handling procedures, and Formatted: Font: 12 pt, Bold, Font color: Text 2 low tolerance for contamination Formatted: Font: 12 pt, Bold, Font color: Text • Liquid and solid wastes from the manufacturing processes are collected and ultimately 2 incinerated Formatted: Font: Bold, Font color: Text 2 • Solvents used in these processes will evaporate during the production process. The Formatted: Font: +Body, 11 pt vapors should be collected in local exhaust systems and vented to air pollution control Formatted: Bulleted + Level: 1 + Aligned at: equipment before their release to the environment 0" + Indent at: 0.25" • Wear respiratory protection during spill clean-up, remove all ignition sources Formatted: Font: +Body, 11 pt • In case of a small spill, absorb with inert material such as sand or soil. Collect that Formatted: Font: +Body, 11 pt material and dispose of it appropriately as chemical waste Formatted: Font: +Body, 11 pt • Large spills can be prevented by only using the material in small containers (1 gallon or less). In the event of a spill, the product should be captured, collected, and reprocessed Comment [A98]: http://www.ifc.org/wps/wcm/ connect/bc321500488558d4817cd36a6515bb18/Fin or disposed of according to applicable governmental requirements al%2B- • The majority of the photoresists and anti-reflectant products are applied to silicon %2BSemiconductors%2Band%2BOther%2BElectroni c%2BMnfg.pdf?MOD=AJPERES&id=1323152500561 wafers. Approximately 97% of the applied product will be spinning off the wafer and should be captured as waste for off-site incineration. The product remaining on the Formatted: Font: +Body, 11 pt wafer undergoes heat treatment (baking step) and converts to a film (solvents are Formatted: Font: +Body, 11 pt 72

Formatted ... evaporated). The dry film may consist of non-volatile acrylic polymers, cross-linkers, Comment [A99]: Please insert reference surfactant, stabilizers and other additives. Ca. 50% of the dried film may dissolve during Formatted ... the development step. The dissolved ingredients should be later neutralized in Comment [A100]: http://msdssearch.dow.com/... wastewater-treatment processes, any fluorinated material remaining in the aqueous Formatted ... phase should be removed before being discharged to the aquatic environment. Formatted ... • The industry has implemented process tools to reuse and recycle as well as to incinerate Formatted ... spent liquid along other measures and reports global emissions of PFOS to waste water Formatted to be approximately 6kg/year [WSC, 2011 Report]. In that report, no information on ... emission quantities of the alternative products was provided Formatted ... • For further information, see for example: [ ] Formatted ... Formatted ... No further specific information on BEPBAT/BEP related topics on the processes Formatted ... discussed in this report could be found. Formatted ... Formatted ... Formatted ... BEPBAT/BEP for Etching Agent for Compound Semiconductors and Ceramic Formatted ... Filters Formatted ... • The content of all previous general chapters on BEPBAT/BEP apply and should be Formatted ... utilized Formatted • For general environmental, health, and safety guidelines for semiconductors & other ... Comment [A101]: electronics manufacturing, see [ ] http://www.ifc.org/wps/wcm... • Used etching liquid should be collected for recovery and reuse and/or be sent for Formatted ... suitable waste treatment Formatted ... Formatted ... No further specific information on BEPBAT/BEP related topics on the processes discussed in this Formatted ... report could be found. Formatted ...

Formatted ...

Formatted ... BEPBAT/BEP for Aviation Hydraulic Fluids Formatted ... • The content of all previous general chapters on BEPBAT/BEP apply and should be Formatted utilized ... Formatted • Aviation hydraulic fluids should be disposed of by approved disposal methods in ... accordance with national, federal, state and local guidelines. Presently, the most Formatted ... universally accepted disposal method is incineration in an approved facility. Formatted ... • Partial reclamation of phosphate ester base stock of spent aviation hydraulic fluids is Formatted ... being practiced. There is no approved reclamation system or known practical Formatted ... technology to completely reclaim spent aviation hydraulic fluids for return to aircraft Formatted ... hydraulic system usage. Formatted ...

Formatted No further specific information on BEPBAT/BEP related topics on the processes discussed in this ... report could be found. Formatted ... Formatted ... Formatted ... BEPBAT/BEP for Metal Plating (hard metal plating) Only in Closed-Loop Formatted ... Systems Formatted ... Formatted ... 73

• The content of all previous general chapters on BEPBAT/BEP apply and should be utilized • Utilize suitable combinations of techniques such as cascade rinsing, ion exchange and evaporation Formatted: Font color: Auto • When hot electrolytes with high evaporation rates are used, closing of the material loop Formatted: Justified, Space After: 6 pt can sometimes already be achieved by simple methods such as using a single static rinse in combination with seven rinsing steps in a pumped, very slowly flowing rinsing cascade. But in most cases, an evaporator is required to regain the electrolyte from the rinse water • Use evaporation for drag-out recovery. An example of this technology, which has been used commercially in decorative plating processes for 20 years (Hauser, 2011), is given Comment [A102]: Please include reference in Figure 4-2 Formatted: Font: Calibri, 11 pt

Formatted: Font: Calibri, 11 pt, Font color: Black Formatted: Indent: Left: 0"

Formatted: Font: Calibri, 11 pt, Font color: Black Figure 4-2: Closed loop in decorative chromium plating (Hauser, 2011) Formatted: List Paragraph, Bulleted + Level: 1 + Aligned at: 0.25" + Indent at: 0.5" • Regional weather patterns may affect applicability of evaporation. Cation exchange Formatted: Font: Calibri, 11 pt, Font color: Black resins with high resistance to strong oxidants are used to selectively remove unwanted metal ions Formatted: Font: Times New Roman, 12 pt, Font color: Auto • Closing the loop for process chemicals does not mean being free of wastewater. In fact Formatted: Font: Calibri, 11 pt, Font color: no loop can be held completely closed all the time. Losses of 10–20% of the applied Black PFOS amount into the wastewater cannot be avoided. Formatted: Font: Times New Roman, 12 pt, • Sources for PFOS can be regeneration of ion exchangers, air scrubber effluents, floor Font color: Auto water of the plating plant and carry-over effects. Formatted: Font: Calibri, 11 pt, Font color: Black Formatted: Indent: Left: 0" 74

Figure 4-3 shows a flow diagram of an almost closed system with optimized PFOS adsorption. The system is used in plastic plating processes. The use of evaporators is a costly investment but might be amortized over a few years.

Formatted: Font: Calibri, 11 pt, Bold Formatted: List Paragraph, Bulleted + Level: 1 + Aligned at: 0.25" + Indent at: 0.5" Formatted: Font: Calibri, 11 pt Formatted: Font: Calibri, 11 pt Formatted: Font: Calibri, 11 pt Formatted: Font: Calibri, 11 pt Formatted: Font: Calibri, 11 pt Formatted: Font: Calibri, 11 pt Formatted: Font: Calibri, 11 pt Formatted: Font: Calibri, 11 pt Formatted: Font: Calibri, 11 pt Formatted: Font: Calibri, 11 pt Formatted: Font: Calibri, 11 pt Formatted: Font: Calibri, 11 pt Formatted: Font: Calibri, 11 pt Formatted: Font: Calibri, 11 pt Formatted: Font: Calibri, 11 pt Formatted: Font: Calibri, 11 pt Formatted: Font: Calibri, 11 pt Formatted: Font: Calibri, 11 pt

Formatted: Font: Calibri, 11 pt Figure 4-3: Process and systems engineering for chromium plating on ABS plastics (Schwarz, 2011) Formatted: Font: Calibri, 11 pt • With this combination of recycling of rinse water, ion exchangers, evaporators, air Comment [A103]: Please include reference scrubber, and finally a two-step adsorption unit, a return or elimination of PFOS by > Formatted: Font: Calibri, 11 pt 99% can be permanently achieved. The separation of PFOS using activated carbon or ion Formatted: Font: Calibri, 11 pt exchangers is realized at a central point in the conventional process of chromium (VI) Formatted: Font: 11 pt reduction (Schwarz, 2011). Formatted: Indent: Left: 0" Formatted: Font: 12 pt, Bold, Font color: Text No further specific information on BEPBAT/BEP related topics on the processes discussed in this 2 report could be found. Formatted: Indent: Left: 0.25" Formatted: Font: 12 pt, Bold, Font color: Text 2 Formatted: Font: 12 pt, Bold, Font color: Text BEPBAT/BEP for Certain Medical Devices (such as ethylene tetraethylene 2 copolymer (ETFE) layers and radio opaque ETFE production, in vitro-diagnostic Formatted: Font: 12 pt, Bold, Font color: Text medical devices, and CCD colour filters) 2 • The content of all previous general chapters on BEPBAT/BEP apply and should be Formatted: Font: 12 pt, Bold, Font color: Text utilized 2 Formatted: Font: Bold, Font color: Text 2 No further specific information on BEPBAT/BEP related topics on the processes discussed in this Formatted: Font: +Body, 11 pt report could be found. Formatted: Normal, No bullets or numbering 75

Formatted: Indent: Left: 0" Formatted: Font: 11 pt BEPBAT/BEP for Fire Fighting Foam Formatted: Font: 12 pt, Bold, Font color: Text 2 • The content of all previous general chapters apply and should be utilized Formatted: Font: 12 pt, Bold, Font color: Text 2 • For a brief overview on BEPBAT/BEP in this industry, please see [Industrial Fire Journal, Spring 2014, p. 24 and 25] Formatted: Font: Bold, Font color: Text 2 Formatted: Font: 11 pt AFFF products are extremely effective in protecting lives and property, and this guidance is not Formatted: List Paragraph, Bulleted + Level: 1 + Aligned at: 0" + Indent at: 0.25" intended to discourage the use of AFFF for fire protection services. There are numerous available techniques and environmental practices, however, that can be employed to minimize Formatted: Font: +Body, 11 pt the possibility of unintended or unnecessary releases and mitigate impacts in the event that an Formatted: Font: +Body, 11 pt incident occurs. Finally, residual materials could be appropriately managed. Comment [A104]: Please include this reference 4.1.1 Inventory management Formatted: Font: +Body, 11 pt Inventory identification Formatted: Indent: Left: 0" A list of fire protection systems and associated types and amounts of AFFF used in each system or piece of equipment may be developed and maintained. Such a list could be helpful in identifying PFOS-based foams should it become necessary to remove them from service or inventory. When product identification is uncertain, the services of an analytical laboratory may be helpful. Product information sheets (i.e. MSDS) should be available at a facility where AFFF is in use. This information could be vital in the event of an incident. Containers or storage vessels could be clearly marked and the contents and type of foam listed. Inventory review It is important to periodically review the inventory of fixed and portable systems that contain AFFF in order to determine the ongoing need for use of these products in each specific location. Over time, use and fire protection classification of areas can change significantly. As appropriate, fire protection personnel would be involved in these determinations. AFFF that is no longer needed at any given facility or location could be removed and appropriately disposed of. As part of this review, the age of products in the inventory could be considered along with the possibility of replacement by newer products. 4.1.2 Training with foams Training of emergency response personnel is a critical step to ensure that timely and appropriate actions can be taken in the event of an emergency. Relative to practice exercises on extinguishing fires, practice foams that do not contain fluorosurfactants can be readily available and used in appropriate circumstances. 4.1.3 Prevention of unintended releases It is important that unintended or unnecessary releases to the environment be minimized as much as possible. Towards this end, this section includes a list of actions that can be applied to help prevent an unintended release at a facility and/or mitigate the impacts of such a release to the environment.

Secondary containment • Review adequacy and integrity of secondary containment systems that may be utilized in the event of a potential release. • Upgrade these systems, as necessary, based on the assessment performed. Testing of fire protection systems • Review procedures to test fire protection systems and modify as needed to ensure containment or capture of any AFFF-containing solution. • Avoid releases to sewers or soils during testing activities. • Consider the use of surrogate fluids when testing the proportioning accuracy of hardware in fire protection systems. This can be an effective method to reduce releases to sewers and may also reduce the cost of testing. Evaluation of sprinkler systems • Survey sprinkler systems to identify the potential for accidental discharge. Consider areas where sprinkler heads could be physically damaged (e.g. vehicular traffic). Evaluate the potential for ambient air temperature or system pressure excursions to trigger a discharge. • Evaluate options and make changes as deemed necessary. Preventative maintenance • Regularly perform preventative maintenance on sprinkler systems, including backflow prevention valves. Emergency procedures • Establish/modify site-specific emergency procedures to incorporate the options proposed in this guidance (see also section 4.3.4). Training • Conduct training, especially for plant maintenance and emergency response personnel, on this guidance (see also section 4.3.4). Container integrity • Regular inspection of containers and vessels (tanks) used to store AFFF concentrate. Integrity of related secondary containment areas could also be included in this procedure. • Record inspection results. 4.1.4 Response to a release Response actions The following guiding principles could be used for responses to an AFFF release: • Minimize intentional release of material or rinse water onto soil. • Avoid discharge of released material or rinse water into a sanitary or storm sewer. • Minimize the volume of impacted materials to the greatest extent possible. • Sites should develop a mitigation plan and evaluate their storm water/accidental release plans.

These principles could also be incorporated into a facility’s emergency response plans and procedures. Again, execution of this guidance should not compromise protection of life or property in the event of an emergency. The initial response to a release can be critical in terms of minimizing possible impacts. Possible immediate actions that could be taken following a release to prevent/mitigate the migration of the release into the environment include: • Use close containment or isolation valves • Use secondary containment • Place released material into secure containers as soon as possible (if plausible) • Build a dam to contain/control run-off • Block a trench • Install a sewer plug • Divert released material into a containment pond • Pump released material into a septic system pumper truck or vacuum truck • Use a defoamer to reduce foam volumes • Place impacted soils on plastic and cover to prevent run-on and run-off • Add adsorbent The above list is only intended to suggest possible actions that could be taken and is not necessarily exhaustive. It would be beneficial that each facility has a site-specific response plan that appropriately considers and incorporates relevant actions and procedures, some of which may be listed above. Documenting a release It is also important to quantify and document any release that occurs including estimations of the amount of AFFF released, the nature of the release (i.e. concentrate or dilute), and the amount of materials impacted (i.e. soil, water, etc.). Two ways to quantify a release from fire protection systems are to: • Calculate the amount based on how long the fire suppression system operated • Measure the amount of AFFF concentrate remaining in the system following the incident and compare it to the inventory before the release Release notification Prompt and appropriate notification concerning a release is another critical element. Notification requirements and procedures would vary depending on where the AFFF release occurred, the nature of the release and governmental reporting requirements (considerations could include potential impacts to drinking water supplies, release to a sensitive environmental area, magnitude of the release, involvement of outside parties, etc.). Site-specific notification requirements and procedures could be clearly outlined in facility emergency response plans and be reviewed as part of routine training. 4.1.5 Management of residual (waste) materials

BAT in dealing with PFOS-based AFFF concentrate and concentrated rinse water is high Comment [A105]: Please include this temperature incineration at a facility designed to handle halogenated waste streams. Small reference volumes of solid materials (soils, absorbent materials, etc.) that contain higher levels of PFOS- Comment [A106]: Please include this based AFFF can be handled in a similar fashion. reference Formatted: Indent: Left: 0" According to experiments on destruction of wastes containing conducted by the Ministry of Environment, Japan, destruction could be done in an incinerator which consists of a primary Formatted: Font: 12 pt, Bold, Font color: Text 2 furnace (a rotary kiln) at temperature of 1,110° C and secondary furnace at temperatures of Formatted: Font: 12 pt, Bold, Font color: Text 900° C, with the combined gas retention time of approximately 8 seconds (Ministry of 2 Environment of Japan, 2013). Formatted: Font: 12 pt, Bold, Font color: Text When PFOS-based AFFF exists in a dilute solution (e.g. collection of water resulting from an 2 accidental triggering of a sprinkler system), treatment using granular activated carbon may be Formatted: Font: 12 pt, Bold, Font color: Text 2 an option. Carbon vendors can be contacted for assistance if the treatment is to occur on site. Formatted: Font: 12 pt, Bold, Font color: Text In situations where dilute PFOS-based AFFF has been applied on top of fuel to prevent or 2 extinguish a fire, the analysis of potential residual management options can become quite Formatted: Font: 12 pt, Bold, Font color: Text complex. Treatment using granular activated carbon may be a viable option although pre- 2 treatment steps may be required to extend the life of the carbon in removing Formatted: Font: 12 pt, Bold, Font color: Text perfluorochemicals. Use of reverse osmosis coupled to electrocoagulation-filtration has also 2 recently been reported as a possible means to treat fire fighting water (Baudequin et. al., 2011). Formatted: Font: 12 pt, Bold, Font color: Text 2 There is ongoing research to develop innovative treatment technologies to remove PFCs from Formatted: Font: 12 pt, Bold, Font color: Text wastewater streams (see Herrera, 2008; Senevirathna, 2010). 2 Formatted: Font: Bold, Font color: Text 2 No further specific information on BEPBAT/BEP related topics on the processes discussed in this Formatted: Font: 11 pt report could be found. Formatted: Font: 11 pt Formatted: Font: +Body, 11 pt Formatted: List Paragraph, Bulleted + Level: 1 BEPBAT/BEP for Insect Baits for Control of Leaf-Cutting Ants from Genus Atta + Aligned at: 0" + Indent at: 0.25" spp. and Acromyrmex spp. Formatted: Font: 11 pt • The content of all previous general chapters apply and should be utilized Formatted: Font: (Default) Lucida Sans Unicode, 14 pt, Bold, Font color: Text 2 • The production of sulfluramid is often carried out in a closed system, with no releases Formatted: Font: (Default) Lucida Sans (discharges, losses, or emissions). The best available process results in a product with purity Unicode, 14 pt, Bold, Font color: Text 2 of at least 98%. Formatted: Font color: Text 2 • Place granular pellets in proper location. Do not overdose Formatted: Font: 12 pt, Bold, Font color: Text • Dispose of left over granular pellets according to information provided by the manufacturer 2 Formatted: Font: 12 pt, Bold, Font color: Text No further specific information on BEPBAT/BEP related topics on the processes discussed in this 2 report could be found. Formatted: Font: 12 pt, Bold, Font color: Text 2 Formatted: Font: 12 pt, Bold, Font color: Text 2 Specific BEPBAT/BEP Measures for Specific Exemptions Formatted ... Formatted ... BEPBAT/BEP for Photo Masks in the Semiconductor and Liquid Crystal Display Formatted ... (LCD) Industries Formatted ... • The content of all previous general chapters on BEPBAT/BEP apply and should be Formatted: Font: Bold, Font color: Text 2 utilized Formatted: Font: +Body, 11 pt 79

• For general environmental, health, and safety guidelines for semiconductors & other electronics manufacturing, see [ ] Comment [A107]: http://www.ifc.org/wps/wcm • Liquid waste from the etching process contains chromium-VI and PFOS. Both these /connect/bc321500488558d4817cd36a6515bb18/Fi nal%2B- substances should be removed from waste water before it is released to the %2BSemiconductors%2Band%2BOther%2BElectroni environment. c%2BMnfg.pdf?MOD=AJPERES&id=1323152500561

• The solid, PFOS containing waste should be disposed of according to guidance provided by the Basel Convention [insert link]. Comment [A108]: Please include reference from earlier No further specific information on BEPBAT/BEP related topics on the processes discussed in this Formatted: Font: +Body, 11 pt report could be found. Formatted: Indent: Left: 0" Formatted: Indent: Left: 0"

BEPBAT/BEP for Metal Plating (hard metal plating) Formatted: Font: 12 pt, Bold, Font color: Text For general information on Best Environmental Practices in the Surface Treatment of Metals and 2 Plastics industry, please see a document published by the European Commission’s Integrated Formatted: Font: 12 pt, Bold, Font color: Text 2 Pollution Prevention and Control Group [ ]. Formatted: Font: 12 pt, Bold, Font color: Text • The content of all previous general chapters on BEPBAT/BEP apply and should be 2 utilized Formatted: Font: 12 pt, Bold, Font color: Text • Consider operating closed-loop systems (see Chapter 4E) 2 Formatted: Font: Bold, Font color: Text 2 • There might be additional BEPBAT/BEP measures to consider related to Chromium-VI Formatted: Normal, Justified, Space After: 6 which are important but outside the scope of this document pt, Tab stops: 0.5", Left • Controlling the electroplating process can lead to reducing PFOS emissions by 50% (IPPC, Comment [A109]: http://eippcb.jrc.ec.europa.e 2006). To better control the process: u/reference

o Measure surface tension of the electrolyte Formatted: Font: (Default) Calibri, Bold, English (United Kingdom) o Measure ampere hour rate o Determine a certain defined surface throughput Formatted: Bulleted + Level: 1 + Aligned at: 0.25" + Indent at: 0.5" o Measure foam stability • In addition, maximize water-reduced rinsing, extensive material recycling and low carry- Comment [A110]: Please include reference over losses by transportation, as well as the reduction of material losses due to process- Formatted integrated measures (IPPC, 2006). Formatted: List Paragraph, Space After: 6 pt, Bulleted + Level: 2 + Aligned at: 0.75" + • When the chrome plating solution is spent, the bath is exhausted and the plating Indent at: 1" solution liquid must be disposed of. The spent solution needs to be treated at a Formatted: Font: (Default) Calibri, Bold chemical waste water treatment plant, where the chromium is precipitated as Formatted: List Paragraph, Justified, Space chromium (III) hydroxide. The resulting dewatered sludge needs to be disposed of at After: 6 pt, Bulleted + Level: 1 + Aligned at: specially prepared landfills, engineered to prevent leakage, where the sludge is stored.7 0.25" + Indent at: 0.5" The practice to use this sludge as a fertilizer for agricultural soil can result in broad scale Formatted: Font: (Default) Calibri, Bold contamination of agricultural fields and provides a major emission source to food and Formatted: Font: (Default) +Body, 11 pt, water and should no longer be practiced.8 English (United Kingdom) Formatted: Bulleted + Level: 1 + Aligned at: 0.25" + Indent at: 0.5", Don't adjust space between Latin and Asian text Formatted: Font: +Body, 11 pt 7 IPPC BREF BAT for the Surface Treatment of Metals and Plastics European Formatted: Font: (Default) +Body, 11 pt, Commission, 2006. English (United States) 8 Krofges P, Skutlarek D, Farber H, Baitinger C, Godeke I, Weber R., PFOS/PFOA Contaminated Megasites In Germany Polluting The Drinking Water Supply Of Millions Of People Organohalogen Compounds Vol. 69 (2007). 80

No further specific information on BEPBAT/BEP related topics on the processes discussed in this Formatted: Indent: Left: 0" report could be found. Formatted: Font: 12 pt, Bold, Font color: Text 2 Formatted: Font: 12 pt, Bold, Font color: Text 2 BEPBAT/BEP for Metal Plating (decorative plating) Formatted: Font: 12 pt, Bold, Font color: Text • The content of all previous general chapters on BEPBAT/BEP apply and should be utilized 2 • Consider operating closed-loop systems (see Chapter 4E) Formatted: Font: 12 pt, Bold, Font color: Text 2

Formatted: Font: Bold, Font color: Text 2 No further specific information on BEPBAT/BEP related topics on the alternative process Formatted: List Paragraph, Bulleted + Level: 1 discussed in this report could be found. + Aligned at: 0" + Indent at: 0.25" Formatted: Indent: Left: 0" Formatted: Font: 11 pt BEPBAT/BEP for Electric and Electronic Parts for Some Colour Printers and Formatted: Font: 12 pt, Bold, Font color: Text Colour Copy Machines 2 • The content of all previous general chapters on BEPBAT/BEP apply and should be utilized Formatted ... Formatted ... No further specific information on BEPBAT/BEP related topics on the processes discussed in this Formatted ... report could be found. Formatted ... Formatted ... Formatted ... BEPBAT/BEP for Insecticides for Control of Red Imported Fire Ants and Formatted ... Termites Formatted ... • The content of all previous general chapters on BEPBAT/BEP apply and should be utilized Formatted ... Formatted ... No further specific information on BEPBAT/BEP related topics on the processes discussed in this Formatted ... report could be found. Formatted ... Formatted ... Formatted ... BEPBAT/BEP for Chemically Driven Oil Production Formatted ... • The content of all previous general chapters on BEPBAT/BEP apply and should be utilized Formatted ... • In addition, consider the following steps: Formatted ... • Step 1: All arrangements put in place to avoid/prevent occupational health and safety Formatted hazards including ensuring the availability and use of personal protective equipment ... (PPE), review of checklist for spillage prevention and control and selection/use of Formatted ... relevant and applicable equipment and machinery. Formatted ... • Step 2: All relevant equipment items including those for stimulation, coil tubing and Formatted ... nitrogen storage and circulation unit mobilized on site. Formatted ... • Step 3: Stimulation equipment is connected to the wellhead and pressure testing is Formatted ... carried out at pressures of up to 4,500 psi for 15 minutes to ensure that system is Formatted ... leakproof. The system is bled off to zero. Formatted ... • Step 4: The injectivity test is carried out by opening the lower master valve on well, 3% Formatted ... NH4Cl is injected and the flow rates recorded against corresponding pressures. This is to ensure that the formation is open enough to accept the acid treated fluid. If injectivity is Formatted ... Formatted ... Formatted: Font color: Black 81

less than 0.5 barrels per minute (bpm) at less than fracture pressure, further assessment of the well will need to be made. • Step 5: Mix the acid treatment as stipulated in the recipes once injectivity of well is established • Step 6: Acidize the formation intervals as follows: • Pump acid preflush (fresh water, corrosion inhibitor, hydrochloric acid, iron sequestering agent, surfactant, mutual solvent and phosphonic complex) • Follow with main treatment flush (fresh water, corrosion inhibitor, surfactant, clay stabilizing agent, iron sequestering agent, phosphonic acid, ammonium fluoride and hydrochloric acid) • Pump after-flush (fresh water, ammonium chloride, mutual solvent, surfactant, fine stabilizer and clay control) • Pump displacement fluid (3% ammonium chloride of tube volume amount) to top of perforation • Step 7: Open the upper master valve gradually and produce immediately the spent acid from the formation and neutralize with soda ash in the flow back tank. If the well does Formatted: Font: Times New Roman, 12 pt not flow naturally, run in the coil tubing to carry out gas lift with nitrogen gas. Formatted: Font: Not Bold • Step 8: The spent liquid in the flow back tank should be treated to remove surfactants Formatted: Indent: Left: 0" and other additives before releasing it to the environment. Remaining solids from the Comment [A111]: This chapter could be spent liquid treatment should be incinerated. expanded with text from the Australian Carpet Institute referenced here. Is this something to consider for the BAT/BEP No further specific information on BEPBAT/BEP related topics on the processes discussed in this Expert Group to take on? report could be found. Formatted: Font: 12 pt, Bold, Font color: Text 2

Formatted: Font: 12 pt, Bold, Font color: Text 2 BEPBAT/BEP for Carpets Formatted: Font: 12 pt, Bold, Font color: Text • The content of all previous general chapters on BEPBAT/BEP apply and should be 2 utilized Formatted: Font: Bold, Font color: Text 2 • For a brief general overview over practices for environmental management, the Carpet Comment [A112]: http://www.carpetinstitute.c Institute of Australia has published a good summary document that provides a detailed om.au/downloads/CodeofPracticeforEnvironmental ManagementVersion1.1.pdf practice audit checklist [ ] Formatted: Font: +Body, 11 pt No further specific information on BEPBAT/BEP related topics on the processes discussed in this Formatted: Indent: Left: 0" report could be found. Formatted: Font: 12 pt, Bold, Font color: Text 2 Formatted: Font: 12 pt, Bold, Font color: Text BEPBAT/BEP for Leather and Apparel 2 Finishing Process Formatted: Font: 12 pt, Bold, Font color: Text • The content of all previous general chapters on BEPBAT/BEP apply and should be 2 utilized Formatted: Font: 12 pt, Bold, Font color: Text 2 • For a reference document on Best Environmental Practices for the tanning of hides and skins, please see a document published by the European Commission’s Joint Research Formatted: Font: Bold, Font color: Text 2 Centre [ ]. Comment [A113]: http://eippcb.jrc.ec.europa.e u/reference

• The products are typically aqueous dispersions of fluorinated polymers that are being Formatted: Font: +Body, 11 pt applied during the fat liquoring process in the tannery (but there might be other points of applications during the wet processing) or aqueous- or solvent-based formulations of fluorinated polymers being applied in an industrial spray coating process. Formatted: Font: +Body, 11 pt, English (United States) No further specific information on BEPBAT/BEP related topics on the processes discussed in this Formatted: Indent: Left: 0.25" report could be found.

Consumer Use • The content of all previous general chapters on BEPBAT/BEP apply and should be Formatted: List Paragraph, Bulleted + Level: 1 utilized + Aligned at: 0.25" + Indent at: 0.5" • Formulations used by consumers are either leather care products in forms of creams, Formatted: Font: +Body, 11 pt lotions or spray. Often spray applications are via aerosol spray (e.g., offered under the Scotchgard® brand and other companies’ brands). Formatted: Font: +Body, 11 pt, English No further specific information on BEPBAT/BEP related topics on the processes discussed in this (United Kingdom) report could be found. Formatted: Indent: Left: 0.25" Formatted: Indent: Left: 0" Formatted: Font: 11 pt BEPBAT/BEP for Textiles and Upholstery Formatted: Font: 12 pt, Bold, Font color: Text • The content of all previous general chapters on BEPBAT/BEP apply and should be 2 utilized Formatted: Font: 12 pt, Bold, Font color: Text 2 • Minimize residual liquors by calculating exactly how much liquor has to be prepared Formatted: Font: 12 pt, Bold, Font color: Text • Optimize process sequences in production to minimize waste between runs 2 • Re-using process liquors has to be done very carefully to avoid causing quality issues Formatted: Font: 12 pt, Bold, Font color: Text that could lead to off-quality goods production. The material supplier can be consulted 2 to test whether re-use is possible Formatted: Font: +Body, Bold, Font color: • Maintain all equipment in excellent working condition and conduct periodic operations Text 2 audits Formatted: List Paragraph, Bulleted + Level: 1 • Optimize drying and curing conditions in the stenter frame + Aligned at: 0.25" + Indent at: 0.5" Formatted: Indent: Left: 0" Additional BAT opportunities to minimize waste and emissions • Use of displacers in the padding device (Foulard) reduces required liquor volume. Formatted: Font: +Body, 12 pt • Automated dosing systems with integrated self-learning systems minimize waste Formatted: Font: +Body by: Formatted: Font: +Body, 12 pt Formatted: Font: +Body o Computing exact pick-up and liquor consumption Mixing only what will be used in the scheduled run Formatted: Font: +Body, 12 pt o Formatted: Font: +Body • Low add-on techniques (such as foam applicators) minimize chemical Formatted: Font: +Body, 12 pt consumption. Formatted: Font: +Body • Where possible, use direct piping into the bath for each of the chemicals to be Formatted: Font: +Body, 12 pt used so that the chemicals are not pre-mixed before being introduced into the Formatted: Font: +Body, 12 pt applicator or machine, and there is no need to clean containers, pumps and pipes before the next step. Formatted: Font: +Body

• Check the input and output flows of the individual processes. Determine the Formatted: Font: +Body, 12 pt input and output mass flows for both the site as a whole and each individual Formatted: Font: +Body production process. Implement a product input check that takes account of raw Formatted: Font: +Body, 12 pt materials, chemicals, dyes and auxiliary materials, etc. Formatted: Font: +Body • Employ improved measurement and control equipment, for example for Formatted: Font: +Body, 12 pt temperature, chemical addition, retention time, moisture (in dryers). Formatted: Font: +Body • Where possible, consider a combination of condensation and scrubbing followed Formatted: Font: +Body, 12 pt by electrostatic precipitation (ESP) or the use of thermal combustion with energy Formatted: Font: +Body recovery on the curing/drying frame/stenters used in processing the fabric. Formatted: Font: +Body, 12 pt • Where possible, consider treatment in wet scrubbers, absorbers, separation via Formatted: Font: +Body Formatted: Indent: Left: 0.25", No bullets or low temperature condensation or combustion to reduce the release of volatile numbering organic compounds from the framing/stenter process. Formatted: Indent: Left: 0" • Where possible, consider exhaust air treatment for emissions-relevant processes Comment [A114]: http://fluorocouncil.com/PD Fs/Guidance-for-Best-Environmental-Practices- . BEP-for-the-Global-Apparel-Industry.pdf For further specific information on BEP for the global apparel industry, please see the document Formatted: Font: +Body, 11 pt published by the Global Industry Council for FluoroCouncil .FluorotechnologyFluoroCouncil Formatted: List Paragraph, Indent: Left: 0"

Formatted: Font: +Body No further specific information on BEPBAT/BEP related topics on the processes discussed in this report could be found. Formatted: Font: 12 pt, Bold, Font color: Text 2

Formatted ... Formatted BEPBAT/BEP for Paper and Packaging ... Formatted • The content of all previous general chapters on BEPBAT/BEP apply and should be ... utilized Formatted: Font: Bold, Font color: Text 2 • For a reference document on Best Environmental Practices for the production of pulp, Comment [A115]: http://eippcb.jrc.ec.europa.e... paper and board, please see a document published by the European Commission’s Joint Formatted ... Research Centre [ ] Formatted: Indent: Left: 0" Formatted: Font: 11 pt No further specific information on BEPBAT/BEP related topics on the processes discussed in this Formatted ... report could be found. Formatted ...

Formatted ... Formatted BEPBAT/BEP for Coatings and Coating Additives ... Formatted • The content of all previous general chapters on BEPBAT/BEP apply and should be ... utilized Formatted: Font: Bold, Font color: Text 2 Formatted: Font: +Body, 11 pt No further specific information on BEPBAT/BEP related topics on the processes discussed in this Formatted: Indent: Left: 0.25" report could be found. Formatted: Indent: Left: 0" Formatted ... Formatted ... BEPBAT/BEP for Rubber and Plastics Formatted ... • The content of all previous general chapters on BEPBAT/BEP apply and should be Formatted ... utilized Formatted: Font: Bold, Font color: Text 2 Formatted: Font: +Body, 11 pt 84

No further specific information on BEPBAT/BEP related topics on the processes discussed in this report could be found.

Formatted: Font: +Body, 12 pt Formatted: List Paragraph, Outline numbered + Level: 7 + Numbering Style: 1, 2, 3, … + Start at: 1 + Alignment: Left + Aligned at: 5.3" + Tab after: 5.55" + Indent at: 5.55" Formatted: Font: +Body

3. BAT/BEP principles for chemicals management of PFOS

3.1 General BAT/BEP measures This section describes principles, measures and safety precautions that apply to all types of products and industries related to PFOS in the following areas: • Storage, handling, dosing, dispensing and transport • Improved knowledge of the raw materials used • Minimization/optimization of the chemicals used • Equipment

Guidelines that apply only to specific process categories are described in chapter 4.

3.1.1 Storage, handling, dosing, dispensing and transport of PFOS In storing, handling, dosing, dispensing, and transporting PFOS containing-products, caution should be used to ensure: • Proper storage according to the instruction of the material safety data sheet (MSDS). • Proper labelling of containers and equipment in special compartments, containers or locations for toxic and explosive chemicals to avoid leakage and spill. • Dosing and dispensing without spilling in automated dosing systems. • Use of only as much PFOS as essentially needed for the process, by measuring and recording the PFOS consumption.

3.1.2 Improved knowledge of the raw materials used

When handling products and preparations containing PFOS, the following relevant information could be collected and analyzed to plan proper handling: • Auxiliaries and basic chemicals information from the supplier concerning proper storage and handling; and environmental characteristics (COD, BOD5, aquatic toxicity, degree of biodegradation/bioelimination, content of nitrogen, phosphorous, sulphur, adsorbable organic halogens (AOX)-relevant compounds, kind and amount of volatile compounds, emission factor, health and safety aspects). • Information from the supplier concerning types of preparation agents, amounts of residual monomer and solvent contents of the raw materials. • Chemical and physical characteristics to be considered for proper handling.

3.1.3 Minimization/optimization of the chemicals used

Minimization and optimization of PFOS-containing chemicals may be achieved by taking the following into consideration: • Avoiding any kind of applied fluorochemicals and auxiliaries that may have a potential to transform into and emit PFOS. • Using fluorochemicals that do not transform and emit PFOS, and performing regular revising of the recipes that include auxiliaries and chemicals with a high degree of

biodegradation/bioelimination. Low human and ecological toxicity, low volatility and low smell intensity are preferred. • Avoiding surpluses of applied chemicals and auxiliaries. • Avoiding, if possible, add-on devices (spraying, foam application, special padding devices). • Decreasing the use of PFOS or PFOS-related substances to the lowest possible level if unable to replace them.

3.1.4 Equipment

3.2 Water management, off-gas and solid waste management The following measures could be considered for water management, off-gas and solid waste management: • Avoidance of leaks and spills. • Substitution of overflow rinsing or minimization of water consumption in overflow rinsing by means of optimized process control. • Reuse of rinsing baths, especially final rinsing baths. • Reversing of current flows in continuous washing. • Cleaning and recycling of process water in selected low charged wastewater streams. • Operational safety in place to avoid unnecessary exposure and accidents. • Use of low emission preparation agents through the total supply chain where possible. • Use of low emission options. • Separate collection of solid waste that has an unknown quantity of PFOS and related substances. • Storing of this waste in a controlled landfill (i.e. a landfill with no leakage to the surrounding environment). • Reuse and recycling of known “PFC-free” product wastes (RPA association with BRE ENV., 2004). • Irreversible destruction of waste with an unknown quantity of PFOS and related substances at a minimum of 1100 °C. • Avoidance of mixing PFOS-free solutions or wash water with solutions containing PFOS.

Further, technical guidelines for the environmentally sound management of wastes consisting of, containing or contaminated with PFOS have been developed under the Basel Convention and provide detailed guidance on the environmentally sound management of PFOS-containing waste.

• Clear and unambiguous criteria for the rejection of wastes and the reporting of all non- conformances. • A system for identifying the maximum capacity limit of waste that can be stored at the facility. • Visual inspection of the waste IN to check compliance with the description received during the pre-acceptance procedure. For some liquid and hazardous waste, this may not be applicable.

3.3.3 Sampling procedures

Implementation of different sampling procedures for different incoming waste vessels delivered in bulk and/or containers could contain the following items: • Sampling procedures based on a risk approach, which could consider the type of waste (e.g. hazardous or non-hazardous) and the knowledge of the customer (e.g. waste producer). • Relevant physico-chemical parameters of all registered waste materials. • Different sampling procedures for bulk (liquid and solids), large and small containers, and laboratory samplers. The number of samples to be taken should increase with the number of containers. In extreme situations, all small containers must be checked against the accompanying paperwork. The procedure should contain a system for recording the number of samples and degree of consolidation. • Details of the sampling of wastes in drums within designated storage, e.g. the time scale after receipt. • Samples prior to acceptance. • Maintenance of a record at the installation of the sampling regime for each load, together with a record of the justification for the selection of each option. Includes a system for determining and recording. • A suitable location for the sampling points. • The capacity of the vessel sampled (for samples from drums, an additional parameter would be the total number of drums). • The number of samples and degree of consolidation. • Operating conditions at the time of sampling. • A system to ensure that the waste samples are analyzed. • A temporary storage, in case of cold ambient temperatures, to allow sampling after defrosting. This may affect the applicability of some of the above items. 3.3.4 Reception facility

managed to promote rapid management (typically a matter of days or less) to find a solution for that waste. • A clear procedure to deal with wastes when inspection and/or analysis prove that they do not fulfil the acceptance criteria of the plant or do not fit with the waste description received during the pre-acceptance procedure. The procedure includes all measures, as required by the permit or national/international legislation, to: inform competent authorities and safely store the delivery for any transition period or reject the waste and send it back to the waste producer or to any other authorized destination. • Waste in the storage area only after acceptance of the waste. • Clearly marked inspection, unloading and sampling areas on a site plan. • Sealed drainage system. • Qualification and regular training of the personnel involved in the sampling, checking and analysis procedures. • Application of a waste tracking system unique identifier (label/code) to each container at this stage. The identifier will contain at least the date of arrival on site and the waste code.

3.4 Occupational health and safety measures This section describes procedures, equipment and measures related to PFOS handling, special and personal protection when working with PFOS and first aid procedures. 3.4.1 PFOS Handling precautions

Waste disposal: • Always dispose of according to local/national regulations.

Handling and special equipment: • Do not get PFOS-containing products in eyes, on skin or clothing. • Do not take it internally. • Do not breathe vapours. • Keep away from heat, sparks, and open flames.

Storage requirements: • Store in a cool dry place away from heat, sparks, and open flames. • Store in a well-ventilated area.

3.4.2 Special and personal protection: PFOS

• Mechanical ventilation: the use of mechanical ventilation is recommended whenever the PFOS-containing product is used in a confined space. Otherwise, assure use in an area where there is natural air movement. • Respiratory protection: in operations where the vapour can be released, wear a respirator with organic vapour canister or cartridge. • Protective gloves: rubber or neoprene. • Eye protection: goggles. • Additional protective equipment: eyewash bottles or other rinsing equipment should be accessible.

3.4.3 First aid procedures

For inhalation: • Remove to fresh air. • If breathing has stopped, give artificial respiration. • Keep body warm and quiet and get medical attention.

Formatted: No bullets or numbering, Don't 4. Specific BAT/BEP measures by process category adjust space between Latin and Asian text

4.1 Coated and impregnated Items BAT and BEP for soil- and water-repellent textile and upholstery applications are: • Use of applied fluorochemicals and auxiliaries with known and less hazardous characteristics that do not contain, transform into or emit PFOS and related substances. • Elimination of the polymer, its side products (impurities) and environmentally sound wastewater treatment considering the behaviour of the degradation products that result in PFOS.

4.1.1 Minimization/optimization of chemicals used

Perfluoroalkyl-based water-and oil-repellent chemicals are not biodegradable. In the past products with a high fluorine content (9-13% wt F) have been used to achieve good effects. These products and the FC-polymers are persistent and also might break down and/or release low-molecular perfluorinated chemicals. Developments during the past years have shown that, with the improved affinity of the perfluorinated chemicals to the applied surfaces, the amount of fluorocarbon that contains the persistent fluorinated carbon chain with the potential of being degraded into PFOS could be significantly reduced without a significant loss of performance. BAT and BEP for these applications are to: • Avoid surplus of applied chemicals and auxiliaries. • Use crosslinking agents that help with the film formation and increase washing durability. • Use extenders with the ability of improving the self-organization of the FC-polymer and safe fluorocarbon-polymer. • Work with proper curing conditions to get an optimum orientation and cross-linking of the fluorocarbon finish on the textile. • Make sure the fabric for the application is free of substances that could disturb the self- organization of the fluorocarbon, such as detergents or rewetting agents. • Avoid spray application if possible.

4.1.2 Application of hydrophobic finish of textiles and upholstery

The following process could be used to minimize the impact on the environment and to secure a safe working environment. Delivery and storage of the product The aqueous emulsions are supplied in drums or intermediate bulk containers (IBCs) and stored in the warehouse of the mill. The product is transported and delivered by truck. Preparation of the application liquor The aqueous emulsion of the polymer is diluted with water in the preparing vessel. The typical concentration is 10–80 g/l.

The worker takes the required amount of product (according to the recipe instructions) from the IBC or container with a bucket and charges it into the preparing vessel. Protective gloves made of nitrile rubber, safety glasses and protective work clothing are recommended as personal protection equipment, without which the worker may be exposed to the PFOS-containing products. After use, the bucket is rinsed with water, which is added to the application liquor and diluted with the residual amount of water. Transfer of the application liquor

The application liquor is transferred using a closed piping system.

Finishing of the fabric

The fabric is immersed in the application liquor and then squeezed off with the padder rolls. The squeezed-off application liquor runs back into the padder (add-on application equipment). Finishing time is approx. 2 to 8 hours, with one worker responsible for process control.

Drying and condensation

The fabric runs into the stenter (drying oven) where it is dried and cured. The typical drying and condensation temperature is between 150° C and 180° C. During this step all volatile components (water and organic solvents) evaporate. It is recommended that the exhaust air, which may contain PFOS-containing vapours, either be released directly into the environment via an exhaust air unit or passed on to an exhaust air washer.

Winding up of the fabric

Behind the stenter the fabric is winded up.

Cleaning of the equipment

The equipment (preparing vessel and padder) is rinsed with small quantities of water. The washing water is normally added to the residual application liquor.

BEP is to reuse the residual application liquor and save it for the next production batch. If this is not possible, it has to be disposed of according to the local or national regulations for industrial wastewater.

The wearing of protective gloves made of nitrile rubber, safety glasses and protective work clothing as personal protection equipment is recommended during the cleaning of equipment.

4.2 Insecticides The production of sulfluramid is often carried out in a closed system, with no releases (discharges, losses, or emissions). The best available process results in a product with purity of at least 98%. Sulfluramid was introduced in Brazil in 1993, after verification of its efficiency with many leaf-cutting ant species, replacing the active ingredient dodecachlor. Currently, the active ingredients used in ant baits are sulfluramid, fipronil and chlorpyrifos. Fipronil and chlorpyrifos are more acutely toxic to mammals, aquatic organisms, fish and bees than sulfluramid.

Comparative studies also demonstrate the low efficiency of ant baits with chlorpyrifos and fipronil. Sulfluramid is the active ingredient in the manufacturing of ant baits in ready-to-use formulations (3 g/kg). Sulfluramid is used as an active ingredient in the manufacturing of ant baits for the control of leaf-cutting ants such as the genus Atta (saúvas) and Acromyrmex (quenquéns), which are the insects that cause the most damage to agriculture. The baits are presented in granular form (pellets), and used in local application next to the holes of the anthill. The ants carry the baits into the nest, incorporating them into the fungus garden. Sulfluramid will stay strongly adsorbed or bounded to the organic matter. An adequate insecticide used to formulate ant baits is lethal at low concentrations and, by ingestion, causes a delayed toxic action. Additionally, it should be odourless and non-repellent, so as to be dispersed by trophallaxis to most workers in the colony. Quick-action products will kill many ants in the first hours following their application, hindering or impairing insecticide distribution throughout the colony. They cause a certain disorder in the anthill and even temporarily stop some of its activities, such as leaf cutting. Granulated baits represent the most widely used method for leaf-cutting ants control, consisting of a mixture of an attractive (usually orange pulp and vegetable oil) and an active ingredient (insecticide), presented in the form of pellets. This method features some significant advantages over other methods. It is a low-cost method that delivers high efficiency with reduced health hazards to humans and the environment during application, and it is specific to the pest target. Its formulation is developed with low concentrations of active ingredients, and its localized application does not require application equipment. Baits are directly applied from their packaging, with no dermal contact, close to active nest entrance holes or anthill trails and carried into the colony by the ants themselves. The utilization of ready-to-use formulations should reduce or impede exposure to humans. BEP for ant baits application could consider the following actions:

• Assessment of infestation in the areas • Estimation of bait consumption • Qualification and periodical training of control teams • Recommendation of method and period for application • Assessment of bait consumption and control efficiency • Elaboration of a database for constant improvement of monitoring

Precautions taken to ensure the safety of appliers concerning health hazards include the use of personal protection equipment, such as boots, gloves, protective masks and long-sleeve overalls, as specified in the product label. Additionally, periodical examinations are adopted, which are included in local or national labour safety rules.

4.3 Fire fighting foam AFFF products are extremely effective in protecting lives and property, and this guidance is not intended to discourage the use of AFFF for fire protection services. There are numerous available techniques and environmental practices, however, that can be employed to minimize

the possibility of unintended or unnecessary releases and mitigate impacts in the event that an incident occurs. Finally, residual materials could be appropriately managed. 4.3.1 Inventory management Inventory identification A list of fire protection systems and associated types and amounts of AFFF used in each system or piece of equipment may be developed and maintained. When product identification is uncertain, the services of an analytical laboratory may be helpful. Product information sheets (i.e. MDSD) could be available at a facility where AFFF is in use. This information could be vital in the event of an incident. It is practical that containers or vessels (tanks) used to store AFFF concentrate are clearly marked concerning their contents. Inventory review It is important to periodically review the inventory of fixed and portable systems that contain AFFF in order to determine the ongoing need for use of these products in each specific location. Over time, use and fire protection classification of areas can change significantly. As appropriate, fire protection personnel would be involved in these determinations. AFFF that is no longer needed at any given facility or location could be removed and appropriately disposed of. As part of this review, the age of products in the inventory could be considered along with the possibility of replacement by newer products. 4.3.2 Training with foams Training of emergency response personnel is a critical step to ensure that timely and appropriate actions can be taken in the event of an emergency. Relative to practice exercises on extinguishing fires, practice foams that do not contain fluorosurfactants can be readily available and used, unless special circumstances warrant otherwise. 4.3.3 Prevention of unintended releases It is important that unintended or unnecessary releases to the environment be minimized as much as possible. Towards this end, this section includes a list of actions that can be applied to help prevent an unintended release at a facility and/or mitigate the impacts of such a release to the environment. Secondary containment • Review adequacy and integrity of secondary containment systems that may be utilized in the event of a potential release. • Upgrade these systems, as necessary, based on the assessment performed. Testing of fire protection systems • Review procedures to test fire protection systems and modify as needed to ensure containment or capture of any AFFF-containing solution. • Avoid releases to sewers or soils need in testing activities. Evaluation of sprinkler systems • Survey sprinkler systems to identify the potential for accidental discharge. Consider areas where sprinkler heads could be physically damaged (e.g. vehicular traffic).

Evaluate the potential for ambient air temperature or system pressure excursions to trigger a discharge. • Evaluate options and make changes as deemed necessary. Preventative maintenance • Regularly perform preventative maintenance on sprinkler systems, including backflow prevention valves. Emergency procedures • Establish/modify site-specific emergency procedures to incorporate the options proposed in this guidance (see also section 4.3.4). Training • Conduct training, especially for plant maintenance and emergency response personnel, on this guidance (see also section 4.3.4). Container integrity • Regular inspection of containers and vessels (tanks) used to store AFFF concentrate. Integrity of related secondary containment areas could also be included in this procedure. • Record inspection results. 4.3.4 Response to a release Response actions The following guiding principles could be used for responses to an AFFF release: • Minimize intentional release of material or rinse water onto soil. • Avoid discharge of released material or rinse water into a sanitary or storm sewer. • Minimize the volume of impacted materials to the greatest extent possible. These principles could also be incorporated into a facility’s emergency response plans and procedures. Again, execution of this guidance should not compromise protection of life or property in the event of an emergency. The initial response to a release can be critical in terms of minimizing possible impacts. Possible immediate actions that could be taken following a release to prevent/mitigate the migration of the release into the environment include: • Use close containment or isolation valves • Use secondary containment • Place released material into secure containers as soon as possible (if plausible) • Build a dam to contain/control run-off • Block a trench • Install a sewer plug • Divert released material into a containment pond • Pump released material into a septic system pumper truck or vacuum truck • Use a defoamer to reduce foam volumes • Place impacted soils on plastic and cover to prevent run-on and run-off • Add adsorbent

The above list is only intended to suggest possible actions that could be taken and is not necessarily exhaustive. It would be beneficial that each facility has a site-specific response plan that appropriately considers and incorporates relevant actions and procedures, some of which may be listed above. Documenting a release It is also important to quantify and document any release that occurs including estimations of the amount of AFFF released, the nature of the release (i.e. concentrate or dilute), and the amount of materials impacted (i.e. soil, water, etc.). Two ways to quantify a release from fire protection systems are to: • Calculate the amount based on how long the fire suppression system operated • Measure the amount of AFFF concentrate remaining in the system following the incident and compare it to the inventory before the release Release notification Prompt and appropriate notification concerning a release is another critical element. Notification requirements and procedures would vary depending on where the AFFF release occurred, the nature of the release and governmental reporting requirements (considerations could include potential impacts to drinking water supplies, release to a sensitive environmental area, magnitude of the release, involvement of outside parties, etc.). Site-specific notification requirements and procedures could be clearly outlined in facility emergency response plans and be reviewed as part of routine training. 4.3.5 Management of residual (waste) materials

Specific actions relative to the management of waste are determined on a case-by-case basis. Guidance on environmentally sound management of wastes consisting of, containing or contaminated with PFOS is available under the Basel Convention. BAT in dealing with AFFF concentrate and concentrated rinse water is high temperature Formatted: Left incineration at a facility designed to handle halogenated waste streams. Small volumes of solid materials (soils, absorbent materials, etc.) that contain higher levels of AFFF can be handled in a similar fashion. According to experiments on destruction of wastes containing conducted by the Ministry of Environment, Japan, destruction could be done in an incinerator which consists of a primary furnace (a rotary kiln) at temperature of 1,110° C and secondary furnace at temperatures of 900° C, with the combined gas retention time of approximately 8 seconds (Ministry of Environment of Japan, 2013). When AFFF exists in a dilute solution (e.g. collection of water resulting from an accidental triggering of a sprinkler system), treatment using granular activated carbon may be an option. Carbon vendors can be contacted for assistance if the treatment is to occur on site. In situations where dilute AFFF has been applied on top of fuel to prevent or extinguish a fire, the analysis of potential residual management options can become quite complex. Treatment using granular activated carbon may be a viable option although pre-treatment steps may be required to extend the life of the carbon in removing perfluorochemicals. Use of reverse osmosis coupled to electrocoagulation-filtration has also recently been reported as a possible means to treat fire fighting water (Baudequin et. al., 2011).

There is ongoing research to develop innovative treatment technologies to remove PFCs from wastewater streams (see Herrera, 2008; Senevirathna, 2010). Formatted: Space After: 6 pt

Formatted: Normal, No bullets or numbering 4.4 Decorative and hard metal plating process Current BAT and BEP means either using PFOS when closing the loop very closely so that hardly Formatted: Left, Tab stops: Not at 0.5" any emissions take place (Schwarz, 2011) or using non-fluorinated readily degradable surfactants. Other polyfluorinated alternatives could only be considered as BAT and BEP if the removal by adsorption technologies or other means were to be considerably improved or the degradation in the environment and/or the ecotoxicological harmlessness was demonstrated. A current research project is investigating adsorbents with the aim of regeneration so that adsorbed PFOS from process water might be recycled back to the process. Conclusively, BAT and BEP are as follows:

Chromium-VI-electrolytes in decorative and hard metal plating: Formatted: Normal, Space After: 6 pt • Provide additional extraction ventilation and/or greater tank enclosure to reduce Formatted: Normal, Left, Space After: 6 pt, the exposure of chromium-VI emission to acceptable levels when using chromium-VI No bullets or numbering both for decorative and hard metal plating. • Apply new technology using chromium-III instead of chromium-VI in decorative metal plating processes. Hard chromium plating: Formatted: Left, Space After: 6 pt • Apply a closed loop system to replace the traditional open system in hard metal Formatted: Normal, Left, Space After: 6 pt, plating processes. No bullets or numbering • Substitute PFOS mist suppressing agent with available non-PFOS agent in hard metal plating processes. Removal of PFOS from the wastewater: Formatted: Left, Space After: 6 pt • Collect and dispose of the waste from the metal plating process using PFOS in an Formatted: Normal, Left, Space After: 6 pt, environmentally sound manner. No bullets or numbering 4.4.1 Chromium-VI-electrolytes in decorative and hard metal plating Formatted: Normal, No bullets or numbering In hard and decorative chrome plating, PFOS is still used because other wetting agents degrade Formatted: Left more or less rapidly under the prevailing, strongly acidic and oxidizing conditions: “In hard chrome plating, PFOS works by lowering surface tension and forming a single foamy barrier on the surface of the chromic acid bath, (see figure 4-1), which maintains its aerosol (fog) formation, thus reducing airborne loss of chromium-VI from the bath and decreasing exposure to this carcinogenic agent” (UNEP/POPS/POPRC.6/13/Add.3, 2010). The same applies for decorative chrome plating. Formatted: Indent: Left: 0", Space After: 6 pt

Formatted: Font: 12 pt Formatted: Left, Indent: Left: 0", Space After: 6 pt, Don't keep with next

Figure 4-1: Foamy barrier on the surface of a chromium bath Formatted: Normal, Space After: 6 pt Formatted: Indent: Left: 0", Space After: 6 pt The aerosol can also be reduced through optimized covering of the chromic acid bath and optimized exhaustion, or enclosure of the baths. 4.4.2 Electroplating of plastics Formatted: Normal, No bullets or numbering In this application, the most commonly used plastic is acrylonitrile butadiene styrene (ABS). It is Formatted: Left etched in a first treatment step to partly remove the butadiene from the surface. Currently a highly concentrated solution of chromic and sulphuric acid is used for that. PFOS is used to enable the acids to make wetting of the water-repellent plastic surface possible. Non-fluorinated surfactants, which are not toxic and easily biodegradable, can be used successfully in the etching process if the production line is very constant. As a precondition, the plastic goods have to be dipped into the surfactant liquid before the etching process. If demands on corrosion resistance and hardness of the surface are low, the physical vapour deposition (PVD) method can replace electroplating processes for decorative applications. 4.4.3 Further electroplating systems Formatted: Normal, No bullets or numbering Other uses of PFOS are the alkaline zinc and zinc alloy plating, the electroless nickel dispersion Formatted: Left, Adjust space between Latin coating and strong acid electrolytes with insoluble anodes, such as precious metal electrolytes and Asian text (e.g. gold, palladium and rhodium). 4.4.4 Measures to avoid or reduce emissions of PFOS into the environment Formatted: Normal, No bullets or numbering Prevention of PFOS by changing the production technology Formatted: Normal Wherever possible, PFOS-free alternative processes should be used, such as the substitution of Formatted: Left chromium-VI electrolytes by chromium-III electrolytes in decorative chromium plating. In some applications the PVD method can replace electroplating processes. Minimizing input of PFOS in controlled electroplating systems Formatted: Normal

The specific exemption to use PFOS as a wetting agent applies only to controlled electroplating Formatted: Left systems. Such a system can only be considered as controlled if PFOS is dosed as a function of a measured value for a certain purpose. This is often not the case in practice. Although great efforts are often undertaken to reduce the PFOS output, the input side is often considered much less accurately. In some cases, the output can be reduced by up to 50%, only by detailed investigation of PFOS inputs and optimized dosage of PFOS (IPPC, 2006). BAT to optimize dosage of PFOS as a function of includes: • Measured surface tension of the electrolyte (not in etching plastics) Formatted: Normal, No bullets or numbering • The measured ampere hour rate (not electroless nickel and etching plastics) • A certain defined surface throughput • The measured foam stability (only in chromium-VI electrolytes) Closing the material loop Formatted: Normal Maximum water-reduced rinsing, extensive material recycling and low carry-over losses by Formatted: Left transportation, as well as the reduction of material losses due to process-integrated measures, are the precondition for the next steps (IPPC, 2006). Hard chromium plating Formatted: Normal BAT is to close the material loop for hexavalent hard chromium by using suitable combinations Formatted: Left of techniques such as cascade rinsing, ion exchange and evaporation. When hot electrolytes with high evaporation rates are used, closing of the material loop can sometimes already be achieved by simple methods such as using a single static rinse in combination with seven rinsing steps in a pumped, very slowly flowing, rinse cascade. But in most cases, an evaporator is required to regain the electrolyte from the rinse water. Decorative chromium-VI plating Formatted: Normal BAT is to close the loop in decorative chromium plating using evaporation for drag-out recovery. Formatted: Left An example of this technology, which has been used successfully in ecological and economic terms for 20 years (Hauser, 2011), is shown in figure 4-2. Formatted: Left, Space After: 6 pt Formatted: Indent: Left: 0", Space After: 6 pt

100

Formatted: Font: Calibri, 11 pt, Font color: Black Formatted: Indent: Left: 0", Space After: 6 pt, Don't keep with next

Figure 4-2: Closed loop in chromium plating (Hauser, 2011) Formatted: Normal, Space After: 6 pt

Regional weather patterns may affect applicability of evaporation. Cation exchanger resins with Formatted: Left, Adjust space between Latin high resistance to strong oxidants are used to selectively remove unwanted metal ions. Closing and Asian text, Adjust space between Asian text and numbers the loop for process chemicals does not mean being free of wastewater. In fact no loop can be held completely closed all the time. Losses of 10–20% of the applied PFOS amount into the wastewater cannot be avoided. Sources for PFOS can be regeneration of ion exchangers, air scrubber effluents, floor water of the plating plant and carry-over effects. 4.4.5 Removal of PFOS from the wastewater Formatted: Normal, Space After: 6 pt, No bullets or numbering Removing PFOS from the wastewater stream by adsorption Formatted: Normal, Space After: 6 pt By selecting suitable activated carbon and optimized flow rates, up to 99% of PFOS can be Formatted: Left removed from wastewater by adsorption onto activated carbon (Fath, 2008). When using special basic ion exchange resins, a reduction of more than 99% of the initial PFOS concentration can be achieved (Zentralverband Oberflächentechnik, 2011). A combination of weak base and strong base anion exchangers is able to reduce the PFOS concentration to <10µg/l (Neumann, 2011). The recommendations of the Stockholm Convention’s COP5 must be taken into account when using any adsorption method that requires a final destruction of the adsorbent that contains PFOS at the end-of-life so as not to deposit such PFOS-containing wastes improperly. The destruction could be done in a BAT hazardous waste incineration plant at temperatures of at least 1100° C and with a residence time of 2 seconds.

101

Formatted: Left, Space After: 6 pt

Figure 4-3 shows a flow diagram of an almost closed system with optimized PFOS adsorption. Formatted: Left, Indent: Left: 0", Space The use of evaporators is a costly investment but is amortized over a few years. After: 6 pt

Formatted: Font: Calibri, 11 pt, Bold Formatted: Indent: Left: 0", Space After: 6 pt, Don't keep with next

Figure 4-3: Process and systems engineering for chromium plating on ABS plastics Formatted: Normal, Space After: 6 pt (Schwarz, 2011) Formatted: Indent: Left: 0", Space After: 6 pt With this combination of recycling of rinse water, ion exchangers, evaporators, air scrubber, and Formatted: Left, Indent: Left: 0" finally a two-step adsorption unit, a return or elimination of PFOS by > 99% can be permanently achieved. The separation of PFOS using activated carbon or ion exchangers is realized at a central point in the conventional process of chromium (VI) reduction (Schwarz, 2011). Electrochemical decomposition of PFOS in the wastewater stream Formatted: Normal, Left Strongly acidic wastewater streams with a high content of PFOS can be treated by an electrochemical process using lead electrodes in batch mode. PFOS is thereby destroyed by up to 99%. Fluorosurfactants are decomposed to hydrofluoric acid under the reaction conditions. Fluorinated organic degradation products were not detected. The short-chained perfluorobutane sulfonate can only be slightly reduced by electrochemical treatment. Because the efficiency of the electrochemical decomposition is strongly reduced with decreasing concentrations of PFOS, the combination with an adsorption step, as described earlier, is recommended for economic reasons (Fath, 2011). Although electrochemical treatment can be cheaper than adsorption, it is an emerging technology that cannot yet be regarded as general BAT.

102

Photochemical decomposition of PFOS in the wastewater stream Photochemical degradation of PFASs seems to be useful technique because significant photodegradation of PFASs, including PFOS and some alternatives (perfluoroalkyl sulfonates and perfluoroalkyl calboxylates) in the environment was observed recently. Fifteen to sixty percent of PFASs in test solution were decomposed under irradiation period (106 days) of natural sunlight at high altitude mountain. Degradation potency was higher in longer chains PFASs compared to shorter chains (Taniyasu et al., 2013). Furthermore, efficient decomposition of perfluorocarboxylic acids (PFCAs) in water by use of 2- 2- persulphate ion (S2O8 ) was reported. Photolysis of S2O8 produced highly oxidative sulphate radical anions (SO4-), which efficiently decomposed perfluorooctanoic acid (PFOA) and other PFCAs including C4-C8 perfluoroalkyl groups. PFOA at a concentration of 1.35 mM (typical of that in untreated wastewater after an emulsifying process in fluoropolymer manufacture) was 2- completely decomposed by a photochemical system with 50 mM S2O8 after 4 hours of irradiation from a xenonmercury lamp (200W). The major products were F- and CO2 and nearly complete decomposition can be expected (Horii et al., 2005). Potential decomposition using subcritical water Subcritical water with zerovalent metals revealed significant degradation of PFOS in test solution of wastewater. Among tested metals (Al, Cu, Zn, Fe), use of iron led to the most efficient PFOS decomposition. Concentration of PFOS in test solution with iron powder decreased to the less than 2% of original solution after heating at 350 °C for 6hrs. Spectroscopic measurements indicated that PFOS in water markedly adsorbed on the iron surface even at room temperature, and the adsorbed fluorinated species on the iron surface decomposed with rising temperature, with prominent release of F- ions to the solution phase above 250 °C (Horii et al., 2006). This method was also effective in decomposing other perfluoroalkylsulfonates including shorter chain (C2-C6) perfluoroalkyl groups and was successfully applied to the decomposition of PFOS contained in an antireflective coating agent used in semiconductor manufacturing (Horii et al., 2006). 4.4.6 PFOS and alternative chemistry Formatted: Normal, Space After: 6 pt, No bullets or numbering Polyfluorinated substitutes Formatted: Normal, Space After: 6 pt It must be taken into account that, due to its high ability to absorb to the surface of most Formatted: Left materials, PFOS has a “memory effect” and can be found in the wastewater stream of electroplating plants months (or, in some cases, more than a year) after being substituted (Breidenbach, 2009). Ion exchangers, washing water from exhausters and every contact surface must be purified or exchanged as well as the electrolyte liquid itself. One of the most common substitutes in electroplating is 1H,1H,2H,2H-perfluoroctane sulfonic Formatted: Left, Indent: Left: 0", Tab stops: acid. Other names are 6:2-Fluorotelomer sulfonate or (3,3,4,4,5,5,6,6,7,7,8,8,8- Not at 0.59" Tridecafluorooctane-1-sulphonate). It is not fully fluorinated, but the perfluorinated tail is persistent and can be a precursor of perfluorinated carboxylic acids (Wang et al., 2011). Because it is structurally very similar to PFOS, its common name is THPFOS (tetrahydro PFOS). In the environment a decrease in the stable perfluorohexane acid (PFHxA) is found. 9 PFOS alternatives used for chrome plating available in China are: Formatted: Indent: Left: 0", First line: 0", Don't adjust space between Latin and Asian

9 UNEP/POPS/POPRC.6/13/Add.3, 2010 103

• FC-53 (potassium 1,1,2,2-tetrafluoro-2-(perfluorohexyloxo)ethane sulfonate Formatted: Normal, No bullets or numbering • FC-53B (Potassium 2-(6-chloro-1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyloxy)-1,1,2,2- tetraflouroethane sulfonate) • Fumetrol®21 (1H,1H,2H,2H-perfluorooctane sulfonic acid) There is little independent and reliable information available on the toxicological and Formatted: Left ecotoxicological characteristics of these polyfluorinated substitutes or their persistence and degradation products. Nevertheless, these substitutes, and in particular their degradation products, are likely persistent in the environment.

According to the Guidance on Alternatives to Perfluorooctane Sulfonate and its Derivatives, Formatted: Left, Indent: First line: 0" currently, no other surfactant can match the low surface tension of PFOS (UNEP/POPS/POPRC.6/13/Add.3, 2010). Therefore, the quantity required for substitution of PFOS by polyfluorinated surfactants increases considerably, about 3 to 10 times (Pabon, 2002). On the output side it must be taken into account that it is much more difficult to remove THPFOS or PFBS from the wastewater by adsorption.

These alternatives tend to adsorb less to sewage sludge in wastewater treatment plants (e.g. Formatted: Left, Indent: Left: 0", Tab stops: Wang et al., 2011), which could potentially translate into higher releases to the environment Not at 0.59" than when using PFOS. Therefore, deposits to soil and in particular groundwater, as well as surface water could occur and contaminate sources of drinking water. Higher emissions, unknown toxicity and degradation to persistent substances highlight the necessity for a timely detailed assessment of environmental fate and the toxicity of the fluorinated alternatives to PFOS ― to clarify as soon as possible to what extent the currently used fluorinated alternatives can contribute to a solution of the problem. Non-fluorinated substitutes Formatted: Normal, Space After: 6 pt Substitution of PFOS by biologically degradable, non-toxic substances would likely be the final Formatted: Left, Tab stops: Not at 0.5" solution. Non-fluorinated surfactants are successfully used during the production process for hard chrome plating and decorative chrome plating (Bresselschmidt, 2009). They are not toxic and easily biodegradable. Although they are degraded in the chromium electrolyte or etching bath and must be constantly dosed, the costs are not higher than using fluorosurfactants. Trivalent chromium is formed by chemical degradation in the bath, which has to be oxidized to hexavalent chromium by membrane electrolysis. This is BAT and commonly used for chromium solution maintenance (IPPC, 2006). Formatted: Space After: 6 pt

Formatted: Normal, No bullets or numbering 4.5 Chemically driven oil and gas production It is reported that PFOS is being used as surfactants for enhanced oil recovery to recover oil trapped in small pores between rock particles. Oil production in some countries, however, has indicated that there are alternative processes that do not require the use of PFOS. 4.5.1 Well stimulation procedures Formatted: Normal, No bullets or numbering BAT measures include the following: Formatted: Left • Step 1: All arrangements put in place to avoid/prevent occupational health and safety Formatted: Normal, Left, No bullets or hazards including ensuring the availability and use of personal protective equipment (PPE), numbering

104

review of checklist for spillage prevention and control and selection/use of relevant and applicable equipment and machinery. • Step 2: All relevant equipment items including those for stimulation, coil tubing and nitrogen storage and circulation unit mobilized on site. • Step 3: Stimulation equipment is connected to the wellhead and pressure testing is carried out at pressures of up to 4,500 psi for 15 minutes to ensure that system is leakproof. The system is bled off to zero. • Step 4: The injectivity test is carried out by opening the lower master valve on well, 3% NH4Cl is injected and the flow rates recorded against corresponding pressures. This is to ensure that the formation is open enough to accept the acid treated fluid. If injectivity is less than 0.5 barrels per minute (bpm) at less than fracture pressure, further assessment of the well will need to be made. • Step 5: Mix the acid treatment as stipulated in the recipes once injectivity of well is established. • Step 6: Acidize the formation intervals as follows: • Pump acid preflush (fresh water, corrosion inhibitor, hydrochloric acid, iron sequestering agent, surfactant, mutual solvent and phosphonic complex). • Follow with main treatment flush (fresh water, corrosion inhibitor, surfactant, clay stabilizing agent, iron sequestering agent, phosphonic acid, ammonium fluoride and hydrochloric acid). • Pump after-flush (fresh water, ammonium chloride, mutual solvent, surfactant, fine stabilizer and clay control). • Pump displacement fluid (3% ammonium chloride of tube volume amount) to top of perforation. • Step 7: Open the upper master valve gradually and produce immediately the spent acid Formatted: Normal, No bullets or numbering from the formation and neutralize with soda ash in the flow back tank. If the well does not flow naturally, run in the coil tubing to carry out gas lift with nitrogen gas. Formatted: Space After: 6 pt

Formatted: Normal, No bullets or numbering 4.6 Semiconductor industry It is important to be aware that PFOS or its salts are not likely to undergo a chemical Formatted: Left transformation through natural processes and they are bioaccumulative, which means they pose a risk of impairing human health if ingested continuously. Measures could be taken to reduce releases of PFOS or its salts by preventing mixing with water, and by the recovery (or the like) of wastewater. In refill work, take measures to minimize the amount of scattering or run-off, and where scattering or runoff occurs, wipe it up immediately with a cloth (or the like). For wastewater containing PFOS or its salts, take measures to recover the wastewater, to the extent possible. 4.6.1 Leakage recovery Formatted: Normal, No bullets or numbering

105

Regarding waste such as waste liquid, for the company to dispose of its own waste properly, or Formatted: Left to dispose of it by entrusting it to a waste disposal operator, based on applicable acts and ordinances. 4.6.2 Storage of PFOS-containing product Formatted: Normal, No bullets or numbering • Store in a location where only the relevant persons can easily enter. Formatted: Left, Space After: 6 pt, No bullets or numbering • Use a sealed container of solid design from which the PFOS-containing product is not likely to leak or spill, etc. and that is made using material that is not likely to allow seepage. • To prevent the run-off of PFOS by rainwater (or the like), store containers containing Formatted: Left, No bullets or numbering PFOS indoors, and take measures to ensure the floor is concrete or coated with synthetic resin (or the like). 4.6.3 Indication of storage location Formatted: Normal, No bullets or numbering When handling PFOS storage and containers storing PFOS, it needs to be indicated that PFOS is being stored in the defined location. 4.6.4 Transport Formatted: Normal, No bullets or numbering When a business operator handling PFOS (excluding a transport operator to whom transport is entrusted) transports it, it is recommended that measures be taken to prevent a container that stores PFOS from overturning. The container must be able to withstand the physical impact. 4.6.5 Refill Formatted: Normal, No bullets or numbering When refilling the PFOS-containing agent: Formatted: Left, Space After: 6 pt, Tab stops: Not at 0" • Handle PFOS indoors. Formatted: Left, Space After: 6 pt, No bullets or numbering • Minimize refills of PFOS. • Take measures to minimize the amount of scattering or run-off of PFOS. • Prepare in case of scattering or run-off of PFOS. • Prepare a cloth and, where necessary, provide a tray under the containers of PFOS- containing products. • Minimize the amount of PFOS mixing with washing liquid. • Prevent any PFOS from remaining in equipment that uses PFOS and take measures to Formatted: Left, No bullets or numbering recover it as much as possible. 4.6.6 Measures for equipment that uses PFOS Formatted: Normal, Space After: 6 pt, No bullets or numbering A business operator handling PFOS needs to consider the following measures • Equipment that uses PFOS: use material that is not likely to corrode or take effective Formatted: Left, Space After: 6 pt, No measures to prevent corrosion; and try to limit the use of the equipment to only work that uses bullets or numbering PFOS. • Floor on which equipment that uses PFOS is placed: to prevent underground leakage of PFOS, take measures to coat the surface with concrete or synthetic resin.

106

• Where scattering of PFOS is expected: install local ventilation equipment and, to prevent releases into the atmosphere, install a dust collector, scrubber or equipment with a similar function. • Piping from equipment that uses PFOS: use material that is not likely to corrode or take effective measures to prevent corrosion. • Wastewater that contains PFOS: use discharge pipes or drainage ditches made of Formatted: Left, No bullets or numbering material that can prevent underground leakage. Inspection of containers that store PFOS and equipment that uses PFOS Formatted: Normal A business operator handling PFOS needs to regularly inspect the following items: • Any leakage or scattering of PFOS from a container, equipment, or piping. Formatted: Left, Space After: 6 pt, No bullets or numbering • Any damage or corrosion that has occurred to a container, equipment, or piping. • Any crack or fissure in the floor. Formatted: Left, No bullets or numbering A business operator handling PFOS who, as a result of an inspection, has identified an irregularity in a container containing PFOS, or in equipment that uses PFOS, needs to promptly make repairs and take other necessary measures. 4.6.7 Measures to deal with leakage of a container storing PFOS or during refill Formatted: Normal, No bullets or numbering A business operator handling PFOS needs to consider the following measures in the event of a Formatted: Left leakage of PFOS: • Notify the proper regulatory agencies about the leakage of PFOS and promptly take Formatted: Left, Space After: 6 pt, No emergency measures to prevent its spread. bullets or numbering • Recover leaked PFOS. • Place and store recovered PFOS in a sealable container along with the cloth (or the like) Formatted: Left, No bullets or numbering used to wipe up PFOS. 4.6.8 Confirmation of release amounts of PFOS Formatted: Normal, Space After: 6 pt, No bullets or numbering A business operator handling PFOS could consider the following measures: Formatted: Left • Confirm the amount of release of PFOS or its salts by conducting sampling and analysis Formatted: Normal, Left, No bullets or suitable for confirmation of the amount of discharge water from the place of business. numbering • If confirmation of release amounts through sampling and analysis is technically difficult, it can be estimated using the usage amount of PFOS. • If PFOS could be released during refilling, take measures to reduce of release amount of PFOS based on the results of sampling and analysis. • Record the results of the estimated PFOS release. Formatted: Space After: 6 pt Photographic industry Formatted: Normal, Left, No bullets or 4.7 numbering PFOS or its salts used in photographic film for industry (photographic developing work) are not Formatted: Left likely to undergo a chemical transformation through natural processes. They are bioaccumulative and pose a risk towards impairing human health if ingested continuously. Part

107

of BAT/BEP is to endeavour to reduce releases of PFOS or its salts by recovery of developing solution and fixing solution. 4.7.1 Measures pertaining to photographic developing work Formatted: Normal, Left, No bullets or numbering When conducting photographic developing work, a business operator handling photographic Formatted: Left film for industry needs to, consider the following measures: • Recover used developing solution and fixing solution Formatted: Left, Space After: 6 pt, No bullets or numbering • Prepare for spills and leaks where developing solution and fixing solution are used Formatted: Left, No bullets or numbering The same measures as described for the semiconductor industry would also be effective for the Formatted: Left photographic industry.

108

Chapter 5 Best Environmental Practices (BEP) for Chemicals Management

General Guidance / Guideline on Best Environmental Practices (BEP) The following subchapters contain specific areas in relation to the environmental management systems (EMS) that could improve environmental performance of an installation including the increased awareness of the workers/employees handling chemicals. BEP describes the application of the most appropriate combination of environmental control measures and strategies, which includes a behaviour that relates to the continuous improvement of environmental performance. BEP provides the framework for ensuring the identification, adoption and adherence to management options that remain important and can play a role in improving environmental performance of the installation. In general, good housekeeping/management techniques/tools often prevent emissions. The main ecological advantages achieved through the use of BEP management methods include: savings in consumption of: o chemicals/auxiliaries o fresh water o energy minimizing the amount of: o solid waste o ecological loads in wastewater Comment [A116]: Please include this reference o off-gas emissions (might not relate to all processes) Another advantage is an improved workplace situation. Well-trained employees are a Comment [A117]: http://www.ifc.org/wps/wcm /connect/Topics_Ext_Content/IFC_External_Corpor prerequisite for implementing BEP system measures. Limiting factors for improving existing ate_Site/IFC+Sustainability/Sustainability+Framewor equipment also need to be taken into consideration with the application of BEP, e.g. new k/Environmental,+Health,+and+Safety+Guidelines/ equipment has to be rebuilt/modified or installed (automated dosing systems, etc.). These applicability factors can be limited due to the fact that the measures may be too cost-intensive Comment [A118]: “Draft revised general technical guidelines for the environmentally sound or due to technological/logistics or a space problem (Schönberger et al., 2005). For references management of wastes consisting of, containing or on general examples of Good International Industry Practice (GIIP), including environmental, contaminated with persistent organic pollutants” at health, and safety guidelines, please see International Finance Corporation’s website [ ] that also http://www.basel.int/Implementation/TechnicalMa tters/DevelopmentofTechnicalGuidelines/POPs/tabi contains a list of specific industry sector guidelines. d/2381/Default.aspx General technical guidelines for the environmentally sound management of wastes have been developed under the Basel Convention. For a general technical guideline, please see [ ] and for Please ensure to link to the most recent revised document. a detailed guidance on the environmentally sound management of PFOS-containing waste Comment [A119]: “Draft revised technical please see [ ]. guidelines for the environmentally sound management of wastes consisting of, containing or contaminated with perfluorooctane sulfonic acid, its Environmental Management Systems (EMS) salts and perfluorooctanesulfonyl fluoride” at http://www.basel.int/Implementation/TechnicalMa A number of environmental management techniques are determined as BEP. The scope and tters/DevelopmentofTechnicalGuidelines/POPs/tabi nature of an EMS will generally be related to the nature, scale and complexity of the installation, d/2381/Default.aspx and the range of environmental impacts it may have. For example, ISO 14001 sets out criteria Please ensure to link to the most recent revised document. for an EMS [ ]. BEP is to implement and adhere to an EMS that incorporates the following features, as Comment [A120]: http://www.iso.org/iso/hom e/standards/management- appropriate, for individual circumstances: standards/iso14000.htm

109

• Definition of an environmental policy for installation by top management (its commitment is regarded as a precondition for a successful application of other features of the EMS). • Planning and establishing of the necessary procedures. • Implementation of the procedures, paying particular attention to: • Structure and responsibility • Training, awareness and competence • Communication • Employee involvement • Documentation • Efficient process control • Maintenance programme • Emergency preparedness and response • Safeguarding compliance with environmental legislation • Checking of performance and taking of corrective action, paying particular attention to: • Monitoring and measurement • Corrective and preventive action • Maintenance of records • Perform independent (where feasible) internal auditing to determine whether or not the EMS conforms to planned arrangements and has been properly implemented and maintained

Additional EMS Considerations Three additional features are considered as supporting measures; their absence, however, is generally not inconsistent with BEP: • Examination and validation of the management system and audit procedure by an accredited certification body or an external EMS verifier • Preparation and publication (and possibly external validation) of a regular environmental statement describing all the significant environmental aspects of the installation, allowing for year-by-year comparison against environmental objectives and targets as well as with sector benchmarks as appropriate • Implementation and adherence to an internationally accepted EMS This last voluntary step could give higher credibility to the EMS, particularly internationally accepted and transparent standards, such as ISO9001 and ISO14001. Non-standardized systems can in principle be equally effective provided that they are properly designed and implemented.

Specific Education and Training of Employees The following training and education opportunities could be beneficial for raising awareness at work for sound chemical management in general: • Process- and machinery-specific training to increase the level of environmental awareness • Appropriate education of workers concerning handling of chemicals and auxiliaries, especially in case of hazardous substances • Maintenance of technical equipment (machines in production as well as abatement and recovery devices); machinery checking (e.g. pumps, valves, level switches); general

110

maintenance by specialized companies at regular intervals; and checking of the burner air inlet at regular intervals • Leak control of chemicals when stored and during processing • Filter maintenance (periodically cleaning and controlling) • Calibration of equipment for chemicals measuring and dispensing devices

Industrial Considerations It is also important for industry to consider the following potential features of the EMS: • At the plant design stage, give consideration to the environmental impact of the eventual decommissioning of the unit • Give consideration to the development of cleaner technologies • Where practicable, conduct sector benchmarking on a regular basis, including energy efficiency and energy conservation activities, choice of input materials, emissions to air, discharges to water, consumption of water and generation of waste • Ensure the provision of full details of the activities carried out on-site: • Descriptions of the waste treatment methods and procedures in the place of installation • Diagrams of the main plant items that have some environmental relevance, together with process flow diagrams (schematics) • Details on the control system philosophy and how the control system incorporates the environmental monitoring information • Details on how protection is provided during abnormal operating conditions such as momentary stoppages, start-ups, and shutdowns • Instruction manual • Operational diary • Annual survey of the activities carried out and the waste treated, which contains a quarterly balance sheet of the waste and residue streams, including the auxiliary materials used for each site • Have good housekeeping procedures in place, which will also cover the maintenance procedure, and an adequate training programme, covering the preventive actions that workers need to take on health and safety issues and environmental risks • Have a close relationship with the waste producer/holder so that the customers' sites implement measures to produce the required quality of waste necessary for the waste treatment process to be carried out • Have sufficient staff available on duty with the requisite qualifications at all times. All personnel should undergo specific job training and further education

General BEP Measures applicable to handling all chemicals This section describes principles, measures and safety precautions that apply to all types of chemicals and industries handling them. Guidelines that apply to specific process categories are described in the following chapters.

Chemical Knowledge, Storage, Handling, Dosing, Dispensing and Transport

111

In storing, handling, dosing, dispensing, and transporting of any chemical, caution should be used. • Before ordering/receiving any chemical review the Safety Data Sheet (SDS). If possible, avoid CMR (Carcinogenic, Mutagenic, Reproductive Toxin) and PBT (Persistent, Bioaccumulative and Toxic) substances, and substances that can degrade to CMR or PBT substances (see SDS Section 2, 11, and 12) • In case a complete SDS is not available from one supplier, order the product from an alternative supplier that provides a complete SDS • Gather information from your supplier on amounts of residual raw materials, by- products and potential degradation products in the product you intend to order • Reject leaking or dented containers upon receiving • Proper storage according to the instruction of the most up to date material safety data sheet (SDS), preferably in Global Harmonization Standard (GHS) format • Before handling any chemical, review the SDS carefully • Proper labelling of containers and equipment; storage in special compartments, containers or locations for toxic and explosive chemicals to avoid leakage and spill • Dosing and dispensing without spilling in automated dosing systems

Minimization/Optimization of the Chemicals Used • Minimize the use of all chemicals and auxiliary materials • Measure, mix and dose chemicals carefully to avoid losses • Minimize residual, left-over chemicals, by calculating exactly how much is needed for the process step • Substitution of overflow rinsing or minimization of water consumption in overflow rinsing by means of optimized process control • Reuse of rinsing baths, including final rinsing baths • Reversing of current flows in continuous washing • Cleaning and recycling of process water – where possible • Use of low emission preparation agents through the total supply chain where possible • Use of low emission options

Equipment • Use equipment, pipes, valves, etc. that are suited to handle the material (e.g., corrosion resistance) top ensure a long equipment life and to avoid equipment breakdown and leaks • To prevent releases to the environment via air, install dust collectors, scrubbers or similar devices • Collect all waste and leftover chemicals from all processes and dispose of them in accordance to guidance provided in the product SDS and in compliance with local rules and regulations. In general, the drain is not an appropriate outlet for waste.

Leak and Spill Procedure • Follow instructions according to information provided on the SDS • Make such a procedure part of the operator training to enhance preparedness

Emissions Reductions and Waste Management 112

The following measures could be considered for water management, off-gas and solid waste management: • Follow all procedures as outlined above • Adhere to waste disposal methods given in the SDS • For guidance on sound management of waste, please follow guidance provided by the Basel Convention [see above].

Formatted: Normal, Space After: 0 pt 5. Guidance/Guidelines on Best Environmental Practices The following subchapters contain specific areas in relation to the environmental management systems that could improve environmental performance of an installation including the increased awareness of the workers/employees. BEP describes the application of the most appropriate combination of environmental control measures and strategies, which includes a behaviour that relates to the continuous improvement of environmental performance. BEP provides the framework for ensuring the identification, adoption and adherence to management options that nevertheless remain important and can play a role in improving environmental performance of the installation. Indeed, these good housekeeping/management techniques/tools often prevent emissions. The main ecological advantages achieved through the use of BEP management methods include savings in consumption of chemicals/auxiliaries, fresh water and energy; and minimizing the amount of solid waste and ecological loads in wastewater and off-gas. Another advantage is an improved workplace situation. Well-trained employees are a prerequisite for implementing BEP system measures. Limiting factors for improving existing equipment also need to be taken into consideration with the application of BEP, e.g. new equipment has to be rebuilt/modified or installed (automated dosing systems, etc.). These applicability factors can be limited due to the fact that the measures may be too cost-intensive or due to technological/logistics or a space problem (Schönberger et al., 2005).

5.1 Environmental management systems

A number of environmental management techniques are determined as BEP. The scope and nature of an EMS will generally be related to the nature, scale and complexity of the installation, and the range of environmental impacts it may have. BEP is to implement and adhere to an EMS that incorporates the following features, as appropriate, for individual circumstances: • Definition of an environmental policy for installation by top management (its commitment is regarded as a precondition for a successful application of other features of the EMS). • Planning and establishing of the necessary procedures. • Implementation of the procedures, paying particular attention to: • Structure and responsibility • Training, awareness and competence • Communication • Employee involvement • Documentation • Efficient process control

113

• Maintenance programme • Emergency preparedness and response • Safeguarding compliance with environmental legislation • Checking of performance and taking of corrective action, paying particular attention to: • Monitoring and measurement • Corrective and preventive action • Maintenance of records • Perform independent (where feasible) internal auditing to determine whether or not the EMS conforms to planned arrangements and has been properly implemented and maintained. 5.2 Additional EMS considerations Three additional features are considered as supporting measures; their absence, however, is generally not inconsistent with BEP. : • Examination and validation of the management system and audit procedure by an accredited certification body or an external EMS verifier. • Preparation and publication (and possibly external validation) of a regular environmental statement describing all the significant environmental aspects of the installation, allowing for year-by-year comparison against environmental objectives and targets as well as with sector benchmarks as appropriate. • Implementation and adherence to an internationally accepted EMS. This last voluntary step could give higher credibility to the EMS, particularly internationally accepted and transparent standards, such as ISO9001 and ISO14001. Non-standardized systems can in principle be equally effective provided that they are properly designed and implemented. 5.3 Specific education and training of employees

The following training and education opportunities could be beneficial for raising awareness at work for sound chemical management in general: • Process- and machinery-specific training to increase the level of environmental awareness. • Appropriate education of workers concerning handling of chemicals and auxiliaries, especially in case of hazardous substances. • Maintenance of technical equipment (machines in production as well as abatement and recovery devices); machinery checking (e.g. pumps, valves, level switches); general maintenance by specialized companies at regular intervals; and checking of the burner air inlet at regular intervals. • Leak control of chemicals when stored and during processing. • Filter maintenance (periodically cleaning and controlling). • Calibration of equipment for chemicals measuring and dispensing devices.

5.4 Industrial considerations

It is also important for industry to consider the following potential features of the EMS: • At the plant design stage, give consideration to the environmental impact of the eventual decommissioning of the unit. • Give consideration to the development of cleaner technologies.

114

• Where practicable, conduct sectoral benchmarking on a regular basis, including energy efficiency and energy conservation activities, choice of input materials, emissions to air, discharges to water, consumption of water and generation of waste. • Ensure the provision of full details of the activities carried out on-site. A good deal of that is contained in the following documentation: • Descriptions of the waste treatment methods and procedures in the place of installation. • Diagrams of the main plant items that have some environmental relevance, together with process flow diagrams (schematics). • Details on the control system philosophy and how the control system incorporates the environmental monitoring information. • Details on how protection is provided during abnormal operating conditions such as momentary stoppages, start-ups, and shutdowns. • Instruction manual. • Operational diary. • Annual survey of the activities carried out and the waste treated, which contains a quarterly balance sheet of the waste and residue streams, including the auxiliary materials used for each site. • Have good housekeeping procedures in place, which will also cover the maintenance procedure, and an adequate training programme, covering the preventive actions that workers need to take on health and safety issues and environmental risks. • Have a close relationship with the waste producer/holder so that the customers' sites implement measures to produce the required quality of waste necessary for the waste treatment process to be carried out. • Have sufficient staff available on duty with the requisite qualifications at all times. All personnel should undergo specific job training and further education.

115

References Basel Convention. 2014. Draft revised technical guidelines for the environmentally sound management of wastes consisting of, containing or contaminated with perfluorooctane sulfonic acid, its salts and perfluorooctanesulfonyl fluoride. http://www.basel.int/Implementation/TechnicalMatters/DevelopmentofTechnicalGuidelines/P OPs/tabid/2381/Default.aspx Breidenbach H. 2009. Substitution von perfluorierten Netzmitteln in Chrombädern 2009 Oberflächen Polysurfaces No. 6/2009. http://www.polymedia.ch/htdocs/Files/Polysurfaces/OP- archives/2009/OP_2009-06.pdf Bresselschmidt B, Zwingenberg. 2009. Neue Alternativen zu PFOS-haltigen Netzmitteln in galvanischen Chromelektrolyten Galvanotechnik Volume 9 Leuze Verlag. Clement Baudequin, Estelle Couallier, Mohammed Rakib, Isabelle Deguerry, Romain Severac, Martial Pabon; 2011. Separation and Purification Technology 76 275-282. Buck R. C, Murphy P. M, Pabon M. 2011. Chemistry, Properties and Uses of Commercial Fluorinated Surfactants. In Handbook of Environmental Chemistry, Volume 17. Polyfluorinated Chemicals and Transformation Products. Knepper, T. P. Lange, F. T. Eds. Springer 2011. Fath A. 2008. Minimierung des PFT Eintrags in die Galvanikabwässer homepage des Umweltministeriums aden-Wuerttemberg. http://www.um.badenwuerttemberg.de/servlet/is/62019/Abschlussbericht_PFOS.pdf?comman d=downloadContent&filename=Abschlussbericht_PFOS.pdf Fath, A. 2011. Elektrochemischer PFT-Abbau in Galvanikindustrieabwässern und Entwicklung einer PFT-Recyclinganlage http://www.um.badenwuerttemberg.de/servlet/is/84532/Abschlussbericht.pdf?command=downloadContent&filenam e=Abschlussbericht.pdf Hauser H. 2011. Prozessintegriertes Recycling am Praxisbeispiel des dekorativen Verchromens Galvanotechnik Vol.1 Leuze Verlag. Herrera V. 2008. Removal of perfluorooctane sulphonate (PFOS) and related compounds from industrial effluents, doctoral thesis University of Arizona.http://www.scribd.com/doc/25113937/Removal-of-perfluorooctane-sulphonate-PFOS- and-related-compounds-from-industrial-effluents. Horii et al. 2005. Efficient Decomposition of Environmentally Persistent Perfluorocarboxylic Acids by Use of Persulfate as a Photochemical Oxidant. Environ. Sci. Technol. 39: 2383-2388. Horii et al. 2006. Efficient Decomposition of Environmentally Persistent Perfluorooctanesulfonate and Related Fluorochemicals Using Zerovalent Iron in Subcritical Water. Environ. Sci. Technol. 40: 1049-1054.IPPC BREF BAT for textiles, European Commission. 2003. http://eippcb.jrc.es/reference/BREF/txt_bref_0703.pdf IPPC BREF BAT for the Surface Treatment of Metals and Plastics European Commission, 2006. Kara H, Chapman A, Sengstschmid H, Posner S. 2010. A Study to Facilitate the Implementation of the Waste Related Provisions of Regulation (EC) No 850/2004 on Persistent Organic Pollutants. Oakdene Hollins Ltd On behalf of DEFRA (UK. Department for Environment,Food and Rural Affairs).

116

Kissa E. 1994. Fluorinated Surfactants: Synthesis-Properties-Applications. Surfactant Science Series 50, 469. Ministry of the Environment of Japan 2013. Summary of the Guideline on the treatment of wastes containing perfluorooctane sulfonic acid (PFOS), and its salts in Japan. April 2013. Neumann S, Podestá W. 2011. Removal of PFTs from Process Water of Surface Plating Industry by means of Ion Exchangers. JOURNAL OECD, Results of the 2006 Survey on Production and Use of PFOS, PFAS, PFOA, PFCA and their Related Substances and Products/Mixtures Containing these Substances, Organisation for Economic Co-operation and Development, 6-Dec-2006. ENV/JM/MONO, 2006,36.

OECD, OECD Portal on Perfluorinated Chemicals. 2010, Available from: http://www.oecd.org/site/0,3407,en_21571361_44787844_1_1_1_1_1,00.html. Pabon M, Corpart JM. 2002. Fluorinated surfactants: synthesis, properties, effluent treatment. Journal of Fluorine Chemistry 114, 149–156. RPA association with BRE ENV., prepared for Department for Environment, Food and Rural Affairs and Environment Agency for England and Wales. 2004. Perfluorooctane Sulphonate: Risk reduction Strategy and Analysis of Advantages and Drawbacks, Final Report. Schönberger H, Schäfer T. 2005. Best Available Techniques in Textile Industry, Research Report 200 94 329 UBA-FB 000325/e, German Federal Environmental Agency. Schwarz R, Schiffer A, Fischwasser K .2011. Vermeidung von PFT-Emissionen in der Oberflächenveredlung; Vortrag auf der Fachtagung Per- und polyfluorierte Verbindungen und kein Ende – Daten, Trends und neue Erkenntnisse am 24./25.05.2011 beim Bayerischen Landesamt für Umwelt (LfU) in München http://www.lfu.bayern.de/analytik_stoffe/analytik_org_stoffe_perfluorierte_chemikalien/facht agungen/index.htm Senevirathna T.M, Lalantha D.S. 2010. Development of Effective Removal Methods of PFCs (Perfluorinated Compounds) in Water by Adsorption and Coagulation. Doctoral thesis, Kyoto Univeristy, Japan. Taylor C. K. 1999. Fluorinated surfactants in practice. Annual Surfactants Review 1999 2 (Design and Selection of Performance Surfactants), 271-316. Taniyasu et al. 2013. The environmental photolysis of perfluorooctanesulfonate, perfluorooctanoate, and related fluorochemicals. Chemosphere 90: 1686– 1692.UNEP/POPS/COP.3/SC-3/5 2007, http://chm.pops.int/Implementation/BATBEP/DecisionsRecommendations/tabid/186/Default.a spx UNEP/POPS/POPRC.3/20/Add.5. 2007, Risk management evaluation on perfluorooctane sulfonate, http://www.pops.int/documents/meetings/poprc/POPRC3/POPRC3_Report_e/POPRC3_Report _add5_e.pdf UNEP/POPS/POPRC.6/13/Add.3. Report of the Persistent Organic Pollutants Review Committee on the work of its sixth meeting on 06.12.2010. Guidance on alternatives to perfluorooctane sulphonate and its derivatives.

117

http://chm.pops.int/Convention/POPsReviewCommittee/POPRCMeetings/POPRC6/POPRC6Rep ortandDecisions/tabid/1312/Default.aspx Wang N, Liu J, Buck R.C, Korzeniowski S.H, Wolstenholme,B.W, Folsom P.W, Sulecki L.M. 2011. Fluorotelomer sulfonate aerobic biotransformation in activates sludge of waste water treatment plants. Chemosphere 82, 853-858. Zentralverband Oberflächentechnik, ZVO Report, 2011. Vol 1. http://www.zvo.org/fileadmin/zvo/ZVOreport/2011/ZVOreport%202011_1%20Internet.pdf Field Code Changed Zhou Liukun, Zhou Ye, Chen Lihua. 2003. Synthesis of Sulfluramid and Development of Gel Bait, Chinese Journal of Hygienic Insecticides & Equipment 1, 16-19.

118